Flame retardant epoxy resin compositions

ABSTRACT

Plastic compositions containing a three component system consisting of (1) epoxy resin polymer, (2) certain bis-phenoxy compounds having the formula: ##STR1## WHEREIN Z in bromine, m and m&#39; are each integers having a value of 1-5 with the proviso that the total bromine atom content is from 6 to 10, and &#34;T&#34; is a straight or branched chain carbon group having 1 to 4 carbon atoms, and (3) an enhancing agent, hereinafter defined.

RELATED PATENT APPLICATIONS

This application is a continuation-in-part of a copending applicationSer. No. 330,843, filed Feb. 8, 1973.

PRIOR ART

The prior art considered in conjunction with the preparation of thisapplication is as follows: U.S. Pat. No. 1,979,145; U.S. Pat. No.2,130,990; U.S. Pat. No. 2,186,367; U.S. Pat. No. 2,263,444; U.S. Pat.No. 2,329,033; U.S. Pat. No. 2,488,499; U.S. Pat. No. 2,738,351; U.S.Pat. No. 2,797,246; U.S. Pat. No. 2,930,815; U.S. Pat. No. 3,385,819;U.S. Pat. No. 3,549,591; U.S. Pat. No. 3,560,441; U.S. Pat. No.3,649,591; U.S. Pat. No. 3,658,634; U.S. Pat. No. 3,666,692; U.S. Pat.No. 3,686,320; U.S. Pat. No. 3,697,456; U.S. Pat. No. 3,879,345; U.S.Pat. No. 3,717,609; U.S. Pat. No. 3,763,243; U.S. Pat. No. 3,787,506;German Patent No. 891,549; German Patent No. 1,139,636; German PatentNo. 2,054,522; Japanese Patent No. (72) 14,500 (and as cited in Volume77, Chemical Abstracts, column 153737k, 1972); Chemical Abstracts,Volume 13, column 448⁵ ; Chemical Abstracts, Volume 31, column 7045⁹ ;Chemical Abstracts, Volume 52 (1958), column 4543-4544; Journal of theChemical Society, pages 2972-2976 (1963); Journal of the AmericanChemical Society, Volume 57 (1935), pages 572-574 and Volume 76 (1954),page 2993; Journal of the Science of Food and Agriculture, Volume 20(1969), pages 748-754; and Philippine Journal of Science, Volume 34(1927), page 159. All of these publications are to be considered asincorporated herein by reference.

BACKGROUND OF THE INVENTION

The present invention relates to plastic compositions containing anepoxy resin. More specifically, the present invention covers plasticcompositions containing a three component system which consists of anepoxy resin, certain bis-phenoxy compounds (hereinafter defined) asflame retardants for said plastic compositions, and an enhancing agent(hereinafter defined) for said flame retardants.

Epoxy resins and utility thereof are known in the art as exemplified byEpoxy Resins, I. Skeist, (Reinhold Plastics Applications Series),Reinhold Publishing Corporation, New York, 1960, and Modern PlasticsEncyclopedia 1972-1973, Vol. 49: No. 10A, Oct. 1972, pages 38, 40, 147,148, 222E, 222F and 229 through 231 and which publications are in totoincorporated herein by reference.

The need for flame retarding epoxy resins has also been recognized inthe art as exemplified by U.S. Pat. No. 3,347,822 and Modern PlasticsEncyclopedia, ibid, pages 222E, 222F, 229 through 231, and 456 through458 and which publications are in toto incorporated herein by reference.

The prior art has specifically recognized the problems of findingsuitable flame retardants for epoxy resins in view of the fact thatpolymer systems differ substantially in both flammabilitycharacteristics and physical properties and there is no predictabilitywhatsoever from one system to another. Thus in the Norris et al paperentitled "Toxicological and Environmental Factors Involved in theSelection of Decabromodiphenyl Oxide as a Fire Retardant Chemical",Applied Polymer Symposium No. 22, 195-219 (1973), the authors state: "Agrowing recognition of the huge annual toll taken by fire is resultingin more stringent flammability requirements for synthetic polymers in avariety of applications. Because of economic constraints and the need toproduce flame resistant polymers without total replacement of existingmanufacturing processes, increased flame resistance is generallyachieved by incorporation of a fire retardant chemical in the finishedproduct. This chemical is usually based on bromine, chlorine,phosphorus, or nitrogen and may either be chemically reacted orphysically blended into the product. Since polymer systems differmarkedly in both flammability characteristics and physical properties,selection of a suitable flame retardant depends on a variety of factorsthat severely limits the number of acceptable materials."

"A general class of synthetic polymers that require flame retardancybecause of their use in electrical and high temperature applications,but pose severe problems in selecting a suitable flame retardant are thehigh performance thermoplastic resins such as thermoplastic polyesters,polyphenylene oxides, and acrylonitrile-butadiene-styrene (ABS)terpolymers. Some of the most important criteria for an acceptable flameretardant in these applications are:

1. It must be as effective as possible to minimize both cost and effecton polymer properties. Use levels may range up to 15% by weight.

2. It must have sufficient stability to withstand conditions encounteredduring polymer processing and use. Processing conditions (blending,extrusion, and molding) often involve temperatures exceeding 300° C. Theflame retardant must tolerate these conditions without degradation orvolatilazation. Also, attention must be given to hydrolytic stabilityand oxidative degradation, particularly under extended service at hightemperatures.

3. It must be compatible with the base polymer and exert minimal adverseeffect on those properties that give the polymer its value. Some ofthese critical properties are tensile strength, impact strength, heatdeflection temperature, shear strength, and flexural modulus.

4. Finally, the flame retardant must not interfere with attainment ofdesired product esthetics and form."

"Because of the stringest thermal stability requirements, only a veryfew compounds have been identified which can meet the necessaryperformance and economic criteria."

The resultant disadvantages in the utilization of various prior artmaterials as flame retardants, in general, for plastic compositionsinclude, without limitation, factors such as thermal migration, heatinstability, light instability, non-biodegradable, toxicity,discoloration, the large amounts employed in order to be effective, andthe unpredictable end results obtained when using the same material indifferent plastics (note, for example, in Modern Plastics Encyclopedia,ibid, page 650, wherein octabromobiphenyl is suitable for use inpolyolefins as a flame retardant therefor, but is not shown for use (orfunctionally equivalent) as such for the other 27 compositions listedsuch as ABS; polycarbonates, polystyrene, acrylics and polyurethanes).Thus, it can be seen that the field of flame retardancy is highlysophisticated and consequently requires substantial research effort toachieve a particular desired end result.

In conjunction with the rendition of an epoxy resin flame retardant theaforegoing discussion is particularly applicable. Furthermore, it isdesirable that, in addition to the retention of good physicalcharacteristics, three characteristics (one of which is critical) of theproduct (epoxy resin) be within certain defined limitations in order toprovide a functional flame retarded product. These three characteristicsare (1) light stability (as measured, for example, by Δ E color values,hereinafter defined), (2) flame retardancy (as measured, for example, byUL-94, hereinafter defined, and which is a critical characteristic andlimitation), and (3) thermal stability (as measured, for example, bycertain ASTM tests for decomposition and migration, hereinafterdefined). This characteristic of flame retardancy is not an arbitraryitem but is a criteria which is strictly adhered to in the epoxy resinart and hereinafter explained in more detail, with particular referenceto the examples contained herein.

In conjunction with the foregoing discussion, the prior art in generalsuggests the use of halogen-containing materials as "potential" or"possible" flame retardants for plastic materials. However, the priorart also recognizes that any material must be adjudged on a case by casebasis because of the unpredictable results of the end product when anyadditive is incorporated therein. For example, with reference to the useof a halogenated fire retardant in U.S. Pat. No. 3,658,634 attention isdirected to the fact that the patentee specifically points out thedisadvantages in the use of a halogen-containing fire retardant. InColumn 1, lines 14-17, the patentee states: "Therefore, if it ispossible to impart fire-retardancy to the thermoplastic polymers withoutdeteriorating the useful properties of the thermoplastic polymers, theycan be widely used in the field of inertia, construction and electricindustries." In Column 1, lines 26-32 the patentee states: "--thecompounds containing chlorine or bromine atoms to be used asfire-retardant agents, are generally sublimated and therefore, the fireretardant agents are sublimated and lost in the process for producingfire-retardant polymers or in after-finishing processes; accordingly,deteriorations of fire-retardancy or difficulties in use tend to occurmore often than not."

In Column 1, lines 39-44 the patentee states: "--the compoundscontaining chlorine or bromine atoms to be used as fire-retardant agentsare unstable in most cases when exposed to ultraviolet rays." In Column1, lines 59-64 the patentee states: "However, as a matter of fact, onlyvery few fire-retardant polymers can be used in actual practice althoughthey are said to have fire-retardant effects, because there arerestrictions such as the conditions employed in production attributableto the properties of the fire-retardant agent, or to the properties ofthe polymers into which they are to be incorporated."

It can be seen, then, from the foregoing discussion and quoted subjectmatter that the field of flame retardancy is highly sophisticated,unpredictable and requires substantial research to produce an endproduct (plastic composition) which meets the necessary criteria forutilitarian purposes, particularly under the present day governmentstandards. Thus, there is always a demand for a material which willfunction as a flame retardant in an epoxy resin and concurrectly willnot, by incorporation therein, adversely effect the chemical and/orphysical and/or mechanical properties of the resultant epoxy resincontaining plastic composition (herein also referred to as "epoxy resinplastic composition") and also have utility.

The prior art problem of providing a flame retarded epoxy resincomposition having desired chemical, physical and mechanical properties,in addition to functional utility, has now been substantially solved bythe present invention and the above-described disadvantagessubstantially overcome.

Accordingly, one of the main objects of the present invention is toprovide epoxy resin plastic compositions which are flame retarded.

Another object of the present invention is to provide a unique threecomponent system for epoxy resin plastic compositions which will notsubstantially adversely affect the chemical and/or physical and/ormechanical properties of said compositions.

A salient object of the present invention is to provide an epoxy resinplastic composition which has a certain defined flame retardancyproperty.

A further object of the present invention is to provide a flameretardant and an enhancing agent which are economical and easy toincorporate into epoxy resins without being degraded or decomposed as aresult of normal blending or processing operations.

BRIEF DESCRIPTION OF THE INVENTION

It has been found that the foregoing objects can be obtained by the useof a unique three component system, which consists of (a) an epoxy resin(hereinafter defined), (b) certain bis-phenoxy compounds (hereinafterdefined), and (c) an enhancing agent (hereinafter defined) tosubsequently provide flame retarded plastic compositions which exhibitoutstanding chemical, physical and mechanical properties.

It is to be understood that the term "flame retarded" as used hereinrefers and is restricted to a limited definition and that is thereduction in flammability of the plastic composition which contains thethree component system. The criticality of this flame retardancy is morespecifically set forth herein, with particular reference being made topage 19 herein regarding UL 94 classification (sometimes referred toherein as "values").

DETAILED DESCRIPTION OF THE INVENTION

The particular class of bis-phenoxy compounds used in the presentinvention compositions have the formula ##STR2##

In Formula I above, Z is bromine, m and m' are each an integer having avalue of 1 to 5 inclusive with the proviso that the total brominecontent of said compound is six (6) to ten (10) bromine atoms inclusive,and T is (1) a straight chain carbon group having from one to fourcarbon atoms and includes, without limitation, groups such as --CH₂ --;--(CH₂)₂ --; --(CH₂)₃ --; and --(CH₂)₄ --; and (2) a branched chaincarbon group having from two to four carbon atoms and includes, withoutlimitation, groups such as follows: ##STR3## and ##STR4##

It is to be understood that all the compounds falling within Formula Iabove and as heretofore defined are generically described herein as"bis-phenoxy" compounds.

Representative, but without limitation, of said bis-phenoxy compoundsare the following: ##STR5## 1,2-bis(2,4,6-tribromophenoxy) ethane##STR6## 1,3-bis(2,4,6-tribromophenoxy) propane ##STR7##1,4-bis(2,4,6-tribromophenoxy) butane ##STR8##2,2-bis(2,3,4,5-tetrabromophenoxy) propane ##STR9##1,2-bis(2,3,4,5,6-pentabromophenoxy) ethane ##STR10##1,1-bis(2,3,4,5,6-pentabromophenoxy) methane ##STR11##1,1-bis(2,4,6-tribromophenoxy) methane ##STR12##1-(2,3,4,5,6-pentabromophenoxy), 2-(2,4,6-tribromophenoxy) ethane

In general, the bis-phenoxy compounds are prepared by reacting ahalogenated phenol with a halogenated alkane at elevated temperatures inthe presence of a basic material such as alkali metal hydroxides,carbonates, bicarbonates, oxides and hydrides. The preferred alkalimetals are potassium and sodium. Where one desires to increase, forexample, ease of handling the reaction mass, solvents such as ketones(e.g. acetone, methyl ethyl ketone, and methyl iso-butyl ketone),alcohols (e.g. methanol, ethanol, iso-propyl alcohol, butyl alcohol andglycols), or aqueous solvents (e.g. water, a mixture of water andalcohol and a mixture of water and ketone) can be employed. The desiredend product i.e. the bis-phenoxy compound, can be recovered from thereaction mass via various methods known to those skilled in the art.Where the end product requires recovery via crystallization, variousaromatic solvents, such as benzene, toluene, xylene, dichlorobenzene andthe like, can be used.

Specifically, the bis-phenoxy compounds are prepared according to thefollowing reactions: ##STR13##

In the above reaction, X is halogen, preferably bromine, and T is thesame as herein defined.

The above reaction is conducted at temperatures ranging from thefreezing point of the initial reaction mass to the boiling point hereof.Preferably the temperatures are from about 40° C. to about 200° C. andmore preferably from about 50° C. to about 175° C. It is to beunderstood that the reaction can be conducted under sub-atmospheric(e.g. 1/10-8/10 atmospheres) pressure. Preferably, the reaction iscarried out at atmospheric pressure.

The above-described processes can be carried out with conventional,readily available chemical processing equipment. For example, aconventional glass-lined vessel provided with heat transfer means, areflux condenser and a mechanical stirrer can be advantageously utilizedin practicing any of the preferred embodiments of the inventiondescribed in preparing the bis-phenoxy examples set forth herein.

The amount of bis-phenoxy compound employed in the present inventioncompositions is any quantity which will effectively render, inconjunction with the enhancing agent, the epoxy resin containingcomposition flame retardant. In general, the amount used is from about1% to 25% by weight, based on the total weight of the composition.Preferably, the amount employed is from about 1% to about 20% by weight.It is to be understood that any amount can be used as long as it doesnot substantially adversely effect the chemical and/or physical and/ormechanical properties of the end plastic composition. The amountutilized, however, is such amount which achieves the objectivesdescribed herein.

The second component of the three component system, and which iscritical therefor, are certain compounds which when used with thebis-phenoxy compounds promote a cooperative effect therebetween and thusenhance the flame retardancy of the resultant plastic composition ascompared to the flame retardancy of either one component usedseparately. These "enhancing agents" comprise the oxides and halides ofgroups IVA and VA of the Periodic Table, i.e. oxides and halides ofantimony, bismuth, arsenic, tin, lead, germanium, e.g. antimonyoxychloride, antimony chloride, antimony oxide, stannic oxide, stannicchloride, arsenous oxide, arsenous chloride, and the like; and organicand inorganic compounds of phosphorus, nitrogen, boron, and sulfur,e.g., triphenyl phosphate, ammonium phosphate, zinc borate, thiourea,urea, stannic sulfide, and the like and oxides and halides of titanium,vanadium, chromium, manganese, iron, niobium, molybdenum copper, zinc,magnesium, e.g., titanium dioxide, titanium chloride, vandaniumpentoxide, chromic bromide, manganous oxide, molybdenum trioxide,ammonium molybdate; and hydrates of the above, e.g., stannic oxidehydrate, lead hydrate; and combinations thereof. The preferred enhancingagents are the oxides of antimony, arsenic and bismuth. However, anycompound which on decomposition, as by ignition, yields these oxideswould be suitable. Thus some organic antimonates are preferred. Theenhancing agents disclosed in U.S. Pat. No. 3,205,196 are also suitablefor use.

U.S. Pat. No. 3,205,196, column 2, states that "Antimony oxide is theantimony compound that is presently preferred for use in the presentinvention. However, many antimony compounds are suitable, inorganicantimony compounds include antimony sulfide sodium antimonite, potassiumantimonite, and the like. Many organic antimony compounds are suitablesuch as the antimony salts or organic acids and their pentavalentderivatives disclosed in copending application Ser. No. 688,143, filedOct. 4, 1957, now U.S. Pat. No. 2,996,528. Compounds of this classinclude antimony butyrate, antimony valerate, antimony caproate,antimony heptylate, antimony caprylate, antimony pelargonate, antimonycaprate, antimony cinnamate, antimony anisate, and their pentavalentdihalide derivatives. Likewise the esters of antimonous acids and theirpentavalent derivatives disclosed in copending application Ser. No.688,108, filed Oct. 4, 1957, now U.S. Pat. No. 2,993,924, such astris(n-octyl) antimonite, tris(2-ethylhexyl) antimonite, tribenzylantimonite, tris(β-chloroethyl)antimonite, tris(β-chloropropyl)antimonite, tirs(β-chlorobutyl) antimonite and their pentavalentcompounds are the cyclic antimonites such as trimethylolpropaneantimonite, pentaerythritol antimonite, and glycerol antimonite. Thecorresponding arsenic and bismuth compounds can also be employed. "

It is to be understood that such patents as U.S. Pat. No. 3,205,196;U.S. Pat. No. 2,996,528 and U.S. Pat. No. 2,993,924 are to be consideredas incorporated herein by reference for all intents and purposes.Without limitation, preferred enhancing agents include Sb₂ O₃, SbCl₃,SbBr₃, SbI₃, SbOCl, As₂ O₃, As₂ O₅, ZnBO₄, BaB₂ O₄.sup.. H₂ O, 2.sup..ZnO.sup.. 3B₂ O₃.sup.. 3.sup.. 5H₂ O and stannic oxide hydrate. The morepreferred enhancing agent is antimony trioxide.

The amount of enhancing agent employed in the present inventioncompositions is any amount which when used with said bis-phenoxycompounds will promote a cooperative effect therebetween. In general,the amount employed is from about 0.5% to about 15%, preferably fromabout 1% to about 10%, by weight, based on the total weight of plasticcomposition. Higher or lower amounts can be used as long as the desiredend result is achieved.

The third critical component of the three component system is the epoxyresin. (Epoxy resins are also sometimes generically referred to in theart as epoxide resins which contain the epoxide group, also called theepoxy, oxirane, or ethoxyline group, which is a three-membered oxidering.) It is to be understood then that the term epoxy resins as usedherein means those materials which contain, on the average, more thanone epoxide group per molecule; and they are polymerised through theseepoxide groups, using a cross-linking agent (also called a curing agentor hardener), to form a tough three-dimensional network. It is in thiscured form, when all the epoxide groups have reacted, that the resinsare almost always used; in the uncured non-cross-linked state they areof limited utility.

The parent resins can be broadly classified into the following fivechemical groups.

    ______________________________________                                        (i)  Glycidyl ethers                                                                             ##STR14##                                                  (ii) Glycidyl esters                                                                             ##STR15##                                                  (iii)                                                                              Glycidyl amines                                                                             ##STR16##                                                  (iv) Linear aliphatic                                                                            ##STR17##                                                  (v)  Cycloaliphatic                                                                              ##STR18##                                                  ______________________________________                                    

the epoxides in groups (i)- (iii) are usually prepared via acondensation reaction between the appropriate diol, dibasic acid, ordiamine and epichlorohydrin (ECH) with the elimination of a simplemolecule, hydrogen chloride; whereas the epoxidised olefins (groups (iv)and (v)) are formed by an addition reaction--the peroxidation of anolefinic double bond by means of a peracid such as peracetic acid. Themost important group of resins commercially comprises the glycidylethers of dihydroxy compounds; and 95% of all epoxide resins are made bythe interaction of epichlorohydrin (ECH) and diphenylolpropane (DPP).

The preferred epoxy resins which are used in the present invention arethose materials which, based on ethylene oxide, its derivatives orhomologs, form straight chain thermoplastics and thermosetting resins,e.g., by condensation of bisphenol and epichlorohydrin to yield athermoplastic which is converted to a thermoset by active hydrogencontaining compounds, like polyamines and dianhydrides and the like.These epoxy resins are further described in the Encyclopedia of PolymerScience and Technology, Volume 6, pages 209 through 219, IntersciencePublishers/John Wiley & Sons, Inc., New York (1967), and Epoxide Resinsby W. G. Potter, pages 1 through 5, Iliffe Books/Butterworth & Co.,Ltd., London, England (1970). Both of these publications are to beconsidered as incorporated herein by reference.

Thus the epoxy resin used in the present invention compositions is anyepoxy resin herein defined and which one so desires to flame retard. Itis to be understood that the epoxy resin used can be a "virgin"material, i.e. substantially free of additives such as stabilizers,plasticizers, dyes, pigments, fillers, and the like, or the epoxy resincan have additives (such as those mentioned and described herein)already contained therein or added concurrently with or after theaddition of the bis-phenoxy compounds and enhancing agents.

The bis-phenoxy compounds and enhancing agents can be incorporated intothe epoxy resin at any processing stage in order to prepare the presentinvention plastic compositions. In general, this is undertaken prior tofabrication either by physical blending or during the process of formingthe epoxy resin per se. Where one so desires, the bis-phenoxy compoundsand/or enhancing agents may be micronized into finely divided particlesprior to incorporation into the epoxy resin.

It is also within the scope of the present invention to employ othermaterials in the present invention compositions where one so desires toachieve a particular end result. Such materials include, withoutlimitation, adhesion promotors; antioxidants; antistatic agents;antimicrobials; colorants; flame retardants such as those listed onpages 456-458, Modern Plastics Encyclopedia, ibid., (in addition to thenew class of flame retardants described herein); heat stabilizers; lightstabilizers; pigments; plasticizers; preservatives; ultravioletstabilizers and fillers.

In this latter category, i.e. fillers, there can be mentioned withoutlimitation, materials such as glass; carbon; cellulosic fillers (woodflour, cork and shell flour); calcium carbonate (chalk, limestone, andprecipitated calcium carbonate); metal flakes; metallic oxides(aluminum, beryllium oxide and magnesia); metallic powders (aluminum,bronze, lead, stainless steel and zinc); polymers (comminuted polymersand elastomerplastic blends); silica products (diatomaceous earth,novaculite, quartz, sand, tripoli, fumed colloidal silica, silicaaerogel, wet process silica); silicates (asbestos, kaolimite, mica,nepheline syenite, talc, wollastonite, aluminum silicate and calciumsilicate); and inorganic compounds such as barium ferrite, bariumsulfate, molybdenum disulfide and silicon carbide.

The above mentioned materials, including filler, are more fullydescribed in Modern Plastics Encyclopedia, ibid, and which publicationis incorporated herein (in toto) by reference.

The amount of the above described materials employed in the presentinvention compositions can be any quantity which will not substantiallyadversely effect the desired results derived from the present inventioncompositions. Thus, the amount used can be zero (0) percent, based onthe total weight of the composition, up to that percent at which thecomposition can still be classified as a plastic. In general, suchamount will be from about 0% to about 75% and more specifically fromabout 1% to about 50%.

With reference to the present invention plastic compositions describedherein, one of the critical features thereof is the unusually high flameretardancy thereof. The significance of flame retardancy of plasticcompositions is well recognized in the art as heretofor mentioned.However, recent developments in conjunction with the use of flameretardant plastic compositions as judged by the Consumer Product SafetyCommission, require a UL-94 value (hereinafter discussed) of V-O inorder to produce a commercially acceptable article of manufacture. TheConsumer Product Safety Commission is continuing to set mandatorystandards in the field where the plastic compositions are utilized andsince about 1970 have increased the criticality of the UL value ofplastic compositions. In reacting to the Consumer Product SafetyCommission's mandatory standards in this area, the producers of (plasticcomposition) articles of manufacture are now requiring that saidarticles have a V-O value in order to meet new mandatory standards whichare anticipated to be activated by federal legislation shortly. Thus,the significance of a plastic composition having a V-O value is wellrecognized in the art; note Modern Plastics, September 1974, pages 74-77and which publication is to be considered as incorporated herein byreference.

In conjunction with the present invention plastic compositions describedherein, an important feature thereof is the light stability thereof. Thesignificance of light stability of plastic compositions is recognized inthe art, e.g. the publication entitled "The Measurement Of Appearance"by Mr. Richard S. Hunter (Hunter Associates Laboratory, Inc., 9529 LeeHighway, Fairfax, Virginia) 1973. Mr. Hunter has been associated withthe efforts of defining appearance and color since the 1930's and wasfor many years an associate of Gardner who is another authority in thisfield. The following paragraphs from Mr. Hunter's book are set forth inorder to demonstrate this light stability significance.

The Judd-Hunter system "of scales for color difference was based onJudd's uniform chromaticity scales triangle. Judd made an instrumentalstudy of a number of woolen swatches rated by dyers for theiracceptability as commercial color matches to standard. The NBS unit ofcolor difference was designed by Judd to be the maximum differencecommercially acceptable in the textile trade as represented by thesedyers at the time when the study was carried out (Judd, 1939). The NBAUnit generally referred to today is not Judd's 1939 unit, but the Hunter1942 version of the Judd unit with 100 units falling between black andwhite."

"Since 1942 this unit has been used in terms of a number of the opponentcolor scales. In a color scale which is already uniform in its visualspacing of lightness and chromaticity, and which has 100 units betweenblack and white as well as rectangular coordinates for chromaticity,color difference in approximate NBS units can be specified in units ofthat system. The color difference becomes the distance between the twocolors in that color space. With rectangular coordinates, the formulais:

    Δ E= √ΔL.sup. 2 + Δa.sup. 2 + Δb.sup.2

Similarly if only the chromaticity component of difference is desired,the formula is:

    Δ C= √Δ a.sup. 2 + Δb.sup.2

"Following Judd's proposed unit of color difference, Hunter proposed themeasurement of much the same quantity by a photoelectric tristimulusmethod in 1942. In the next year, Scofield proposed a quantity which wasquite a bit easier to compute. Scofield used the reciprocal of thesquare root of reflectance instead of the reciprocal of the fourth rootof reflectance as a multiplier in adjusting reflectance values foruniform lightness scale intervals. This is the only difference betweenthe Scofield and the Judd-Hunter formulas for color difference.(Scofield, 1943)."

"In 1948, Hunter started to develop a tristimulus instrument which wouldread chromaticity dimensions of opponent colors directly. He was seekingto improve the precision and usefulness of results of the tristimulusreflectometers previously used. The R_(d) scales developed in the period1948 and 1950 did not have a uniform lightness readout but did havedirect reading visually uniform a and b scales. The L scales, in whichthere is approximate perceptual uniformity in all three dimensions, werecreated in the period 1950-1952 but were not described in a formalpublication until 1958. These two sets of Hunter Color Difference Meterscales enjoy wide use because of the fact that they can be read directlyfrom a tristimulus instrument with high precision, and offerinstrumental computation of color difference by the ΔE formula givenabove."

"NBS Unit of Color Difference is defined as: the unit of colordifference of the National Bureau of Standards. The unit is about fourtimes as great as the smallest difference observable under idealconditions. Differences of less than one unit are usually not importantin commercial transactions. In Munsell terms, one NBS unit is equivalentto about 0.1 Value step, 0.15 Chroma step, or 2.5 Hue step at Chroma 1."

"Hunter further investigated the use of L', α', β' for color differencemeasurement. He recognized at this time (which no other color-differencescale before or since has recognized) that perceived color differencewill depend on the proximity of the specimens compared and on theirglossiness. Accordingly, the 1942 Hunter color difference equationincludes factors to account for these variables. It is this equation,with selected constants, that defines the widely used NBS unit of colordifference."

"High precision is almost always essential for useful color differencemeasurements. Only with precise instruments is it possible to measurecolor differences as small as those the eye can see. Instrument accuracyis also normally a requisite because spectrally inaccurate instruments,even though precise, will give visually inaccurate color differencemeasurements wherever there are spectral differences between thespecimens involved. The ease of obtaining and interpreting values ofcolor difference is another factor which may affect the selection of aprocedure."

"Twenty years ago, color difference scales were in demand to serve as abasis for setting one-number tolerances for fading and acceptability ofmatches. The Index of Fading and NBS unit were used as units."

"Today, the concept of color difference is more refined. One numbertolerances are seldom used. Instead, color difference tolerances aredesigned as boundaries in color space within which acceptable colorsmust fall. The boundaries do not necessarily correlate withperceptibility of difference but rather with the limits ofacceptability. The standard color, furthermore, may not be in the centerof the bounded region but may be displaced to one side. For example,where subsequent yellowing may occur, the tolerance for the yellow-bluedimension might be +0.1, -0.8 units."

"Color difference specifications are tighter today and tolerances aresmaller. The specification usually treats the color dimensionsseparately so that a complete specification would contain nine numbers:The three numbers that describe the desired color, and the six numbersthat describe the individual plus and minus tolerances. Such tolerancescan be reduced to graphs which not only show acceptability but provide aguide to the formulation correction needed to correct an off shade. Whenthe question of acceptability becomes a question of sorting objectsaccording to shade, a graphical chart showing the classification ofcolor values can be quite helpful."

"Although color measurements are frequently used for identification,sorting and recording of color values, the primary uses of tristimulusinstruments all involve measurements of fairly small color differences.The most frequent uses of these small color difference measurements areto establish closeness to standard and to give guidance for theadjustment of color mismatches. They are also used in the study ofdeterioration in a product as a result of exposure and use."

"Spectrophotometers and tristimulus instruments made up the majority ofcolor appearance measuring instruments in use in industry.Spectrophotometers give wavelength-by-wavelength analyses of thereflecting properties of objects, while tristimulus instruments by theuse of filters which approximate the Standard Observer functions of theeye, give measurements of color in X, Y, Z terms, or in L, a, b values.Spectrophotometers are essential where color formulation is involved,and metamerism must be controlled. However, tristimulus colorimeters andreflectometers provide precise and less expensive means for the routinemeasurement of color and adjustment of small color differences."

In view of the foregoing quoted subject matter, it can thus be seen thata change in ΔE value of 1 unit constitutes a real change. Note alsoJapanese patent application (publication 022,456 of 1974) which showsthat achieving a color change in ΔE of only 2.3 is significant as itpertains to a polycarbonate polymeric composition; (this value issubstantially the same as those ΔE values obtained in polycarbonatetests and which results thereof are shown in Table IX herein, i.e. 2.3versus 2.5 over the control). Both of these publications (i.e. theJapanese patent 022,456 and the Hunter book) are to be considered asincorporated herein by reference. It is to be noted also that a lower ΔEvalue is more desired and the higher ΔE value is least desired. This ΔEvalue is not an abstract value, however, since one must compare it withthe ΔE values of the "control" plastic composition. One of the desiredΔE values would be where both the ΔE values of the "control" plasticcomposition (without additives-i.e. without flame retardant andenhancing agent) and the plastic composition with said additives aresubstantially the same or the latter has a lower value.

EXAMPLE I

An epoxy resin (Epon 828, a product of Shell Chemical Company and thereaction product of bisphenol A and diglycidyl ether) is utilized as thebase resin in order to prepare 26 formulations. With the exception offormulation No. 1, the particular bis-phenoxy compound (and the antimonytrioxide enhancing agent where indicated) is incorporated into the epoxyresin by adding both to the epoxy resin which is contained in a 16 ounceflask in a water bath. This addition occurs during the heat-up of theepoxy resin to approximately 85° C. After the bis-phenoxy (and Sb₂ O₃)addition to and dispersion therein, a hardener(Dow' s DEH 50, 4,4'-methylenedianiline) is added over a period of about 15 minutes inorder to insure dissolution therein.

The resultant mixture is then poured into a mold which consists of two(2) vertically positioned glass plates which are covered with cellophanefilm and separated by a 1/8 inch Teflon gasket. The mold is then placedin an oven and the epoxy resin formulation cured for 16 hours at 55° C.,then 2 hours at 125° C. and finally 2 hours at 155° C. The epoxy resinformulation is then removed from the oven and cooled and then the solidsheet (epoxy resin formulation) is cut to test specifications in orderto provide samples therefor. The percentages by weight of thebis-phenoxy compound and Sb₂ O₃ used in the formulations are listed inTable I.

Portions of the solid samples of each respective formulation (Nos. 1-26) prepared according to the above described procedure are thensubjected to two different standard flammability tests, i.e. UL 94 andASTM D-2863-70. The UL 94 is, in general, the application of a burner toa test specimen (strip) for a certain period of time and observation ofcombustion, burning, and extinguishment. This procedure is fully setforth in Underwriters' Laboratories bulletin entitled UL 94, Standardfor Safety, First Edition, September 1972 and which is incorporatedherein by reference. ASTM No. D-2863-70 is a flammability test whichcorrelates the flammability of a plastic specimen to the availableoxygen in its immediate environment; this correlation is stated as anOxygen Index, O.I., level predicated upon the percent oxygen in thegaseous medium which is required to just provide a steady state ofcontinuous burning of the plastic specimen. The ASTM method is fullydescribed in 1971 Annual Book of ASTM Standards - Part 27, published bythe American Society for Testing and Materials, 1916 Race Street,Philadelphia, Pa.; this publication is to be considered as incorporated(in toto) herein by reference. The UL 94 test is the more critical testas it is the test generally used to determine the suitability ofthermoplastics for commercial applications.

The results of these flammability tests are shown in Table I.

                                      TABLE I                                     __________________________________________________________________________    FLAMMABILITY DATA FOR                                                         EPOXY RESIN PLASTIC COMPOSITIONS                                              CONTAINING BIS-PHENOXY COMPOUNDS,                                             WITH AND WITHOUT ENHANCING AGENTS                                             FORMU-                                                                             BIS-  COM-  ENHANCING                                                                             OXYGEN                                               LATION                                                                             PHENOXY                                                                             POUNDS                                                                              AGENT   INDEX UL 94                                          NO.  FORMULA                                                                             %     Sb.sub.2 O.sub.3, %                                                                   %     VALUE                                          __________________________________________________________________________    1.   --    0     0       27.5  SB                                             2.   III   3.0   0       30.8  SB                                             3.   III   7.5   0       33.0  SB                                             4.   III   10.0  0       33.5  SB                                             5.   III   12.5  0       34.0  SB                                             6.   III   3.0   3       38.0  SE-O                                           7.   III   7.5   3       38.3  SE-O                                           8.   III   10.0  3       38.9  SE-O                                           9.   III   12.5  3       40.0  SE-O                                           10.  III   3.0   5       38.2  SE-O                                           11.  III   7.5   5       38.7  SE-O                                           12.  III   10.0  5       39.5  SE-O                                           13.  III   12.5  5       40.5  SE-O                                           14.  II    3.0   0       30.5  SB                                             15.  II    7.5   0       31.0  SB                                             16.  II    10.0  0       31.5  SB                                             17.  II    12.5  0       32.0  SB                                             18.  II    3.0   3       36.5  SE-O                                           19.  II    7.5   3       37.0  SE-O                                           20.  II    10.0  3       37.3  SE-O                                           21.  II    12.5  3       37.9  SE-O                                           22.  II    3.0   5       37.1  SE-O                                           23.  II    7.5   5       37.4  SE-O                                           24.  II    10.0  5       38.0  SE-O                                           25.  II    12.5  5       38.5  SE-O                                           26.  II    15.0  3       38.0  SE-O                                           __________________________________________________________________________

Referring to Table I, the bis-phenoxy compound formula II or III relatesto the structural formulae heretofor set forth; and the UL 94 values areon a graduated scale wherein the highest degree to lowest degree offlame retardancy is respectively SE-0, SE-1, SE-2, SB and Burns.

The results shown in Table I demonstrate the unique effectiveness of theplastic composition containing an epoxy resin, the bis-phenoxy compound,and the enhancing agent. Specifically, formulation No. 1 (the control)has a O.I. of 27.5 and UL 94 value of SB. Nos. 2-5 and 14-17 show theuse of only the particular bis-phenoxy compound without the enhancingagent, and which still resulted in a UL 94 rating of SB, i.e. like thecontrol.

The use of the three component system, i.e. epoxy resin, bis-phenoxycompound and enhancing agent, is fully demonstrated via the resultsobtained from testing formulation Nos. 6-13 and 18-26. Thus, the use ofan enhancing agent such as Sb₂ O₃ to promote a cooperative effectbetween such agent and the bis-phenoxy compound is quite apparentparticularly when viewing the results obtained from testing formulationNos. 1, 4, and 8. The highest UL 94 ratings are obtained in all caseswith the three component system.

EXAMPLE II

Portions of the solid samples of formulation Nos. 1- 26 preparedaccording to the above-described procedure of Example I are subjected tothe following ASTM Tests in order to ascertain other properties of theresultant plastic composition:

    ______________________________________                                        (1)  Tensile Strength                                                              (at break)      :    ASTM Test No. D638-61T;                             (2)  Flexural Strength                                                                             :    ASTM Test No. D790-63;                              (3)  Flexural Modulus                                                                              :    ASTM Test No. D790-63;                              (4)  Notched Izod Impact                                                                           :    ASTM Test No. D256-56; and                          (5)  Heat Distortion                                                               Temperature (HDT)                                                                             :    ASTM Test No. D648-56.                              ______________________________________                                    

Each of the aforementioned ASTM Tests are standard tests in the art andare utilized collectively in order to ascertain the efficacy of apolymeric system as an overall flame retarded composition for commercialapplication. All of these ASTM Tests are to be considered asincorporated herein by reference.

The results of these ASTM Tests show in general that the physicalproperties of the present invention compositions are basically the same(except O.I. and UL 94 values) as the plastic material without the flameretardant (i.e. formulation No. 1). For example, and with reference toTable I, formulation No. 1 (the control) had a flexural strength of10,460 psi and a heat distortion temperature (HDT) of 306° F. whereas informulation Nos. 2 and 3, 300° F., and in formulation Nos. 6 and 7, theflexural strength was respectively 10,320 psi and 8,830 and the HDT wasrespectively 298° F. and 298° F. It can thus be seen then from this datathat there is no substantial adverse effect on the physical propertiesof the plastic material when the bis-phenoxy compounds and enhancingagents are incorporated therein.

EXAMPLE III

The procedure of Examples I and II are repeated except that thebis-phenoxy compound used corresponds to Formula IV, heretofor setforth, instead of Formulae II and III. Substantially the same resultsare obtained using the Formula IV compound as those obtained usingFormulae II and III compounds.

EXAMPLE IV

The procedure of Examples I, II and III are repeated except that theenhancing agent used is zinc borate instead of Sb₂ O₃. Substantially thesame results are obtained using zinc borate as those obtained using Sb₂O₃. The other enhancing agents are predicted to be equally effective.

EXAMPLE V

Strip samples of each of Formulation Nos. 1 (control) through 26, TableI, are subjected to light stability tests via the use of a"Weather-Ometer", model 25/18 W. R., Atlas Electrical Devices Company,Chicago, Illinois. Utilizing an operating temperature of 145° F. and 50%relative humidity, each strip is subjected to 200 hours of "simulateddaylight" via the use of a carbon arc. The results show that after 200hours, there is no significant discoloration in any strip tested andwhich demonstrates that the present invention compositions are highlyresistant to deterioration by light.

This example is repeated with the exception that a Xenon arc is usedinstead of the carbon arc and the length of time is 100 hours instead of200 hours. The results show, as measured by the Gardner Colorimeter,that the Δ E values of the "control" and epoxy resin, bis-phenoxycompound and enhancing agent--containing compositions-- ranged fromabout 3 to about 8.

EXAMPLE VI

Samples of each of Formulation Nos. 1 (control) through 26 Table I, aresubjected to temperature (thermal) stability tests via the use ofthermal gravimetric analysis (TGA). This test employed the use of a"Thermal Balance", model TGS-1, Perkin-Elmer Corporation, Norwalk,Connecticut, and an electrical balance, Cahn 2580 model, Cahn InstrumentCompany, Paramount, California. The results of these tests show that theepoxy resin, bis-phenoxy compound, enhancing agent--containingFormulations had more than adequate stability for melt processing andsubsequent heat aging (i.e. high temperature applications) and thusdemonstrating that the particular bis-phenoxy/enhancing agentcombinations are quite compatible with the epoxy resin material. Thebis-phenoxy compound stability thus aids in providing sufficient flameretardancy at the epoxy resin decomposition temperature. This test alsodemonstrates that the bis-phenoxy compounds do not exhibit migration.

COMPARATIVE EXAMPLES

The following examples are presented to demonstrate the unpredictabilityof plastic compositions, via the end results, containing the samebis-phenoxy compounds, with or without an enhancing agent.

Referring more specifically to the following examples, Example VIIcompares a three component system, i.e. ABS, certain "bis-phenoxycompounds" (herein referred to as BPC), and enhancing agent with fourother polymers containing the same bis-phenoxy compounds (as used in thepresent invention) and enhancing agent. The four comparative polymersare polyacrylonitrile, polypropylene, nylon and polymethylmethacrylate.As will be seen from the results hereinafter set forth, the four otherpolymers had no flame retardant efficacy when incorporating thebis-phenoxy compounds and enhancing agents, whereas the ABS system didand so demonstrated an unexpected and substantial flame retardantefficacy. These results, thus, are another indication of theunpredictability of additives when incorporated into polymer systems andcorrespond to the subject matter set forth in "Modern PlasticEncyclopedia", ibid., regarding the use of octabromobiphenyl in onepolymer but not shown for use (or functionally equivalent) in numerousother materials.

Referring to Example VIII, this example sets forth the comparison of theuse of the bis-phenoxy compounds in eight polymer systems but insubstantially more detail with particular reference to light stability,flammability and thermal stability. The results disclosed in thisExample VIII are similar to those results obtained in Example VII.

EXAMPLE VII

Regarding Formulation Nos. 1- 10 in Table II, a virgin polyacrylonitrileplastic material, (T-61 polymer crumb, a product of American Cyanamidand characterized as a copolymer of 93% by weight acrylonitrile andabout 7% by weight methyl methacrylate) is utilized as the base resin inorder to prepare 10 formulations (plastic compositions). With theexception of formulation No. 1, the particular bis-phenoxy compound (andthe antimony trioxide enhancing agent where indicated) is incorporatedinto the plastic (which is dried to remove moisture therefrom) by addingboth to a Waring blender which contains acetone as a dispersing liquid.The resultant mixture, after blending for 3 minutes, is poured intoevaporation dishes and the acetone evaporated, first at room temperature(20°-25° C.) for 60 minutes and followed by oven drying at 60° C. forone hour.

The percentages by weight of each component utilized in the respectiveformulations are listed in Table II. Each formulation is discharged fromthe evaporation dish and is ground into powder. The powder is subjectedto compression molding in a Wabash press by placing said powder betweentwo platens, the bottom of which contains four equal size depressionsthree inches by five inches by 1/8 inch deep. The top platen is thenplaced over the bottom platen and heat transfer means supplied theretoin order to melt said powder and thus provide solid samples (aftercooling) for testing. The temperature and ram pressure utilized arerespectively 100° C. and 30 tons.

A polypropylene plastic material, (Hercules Pro-fax® 6523 grade ofpolypropylene) is utilized as the base resin in order to prepare 13formulations (plastic compositions)-- Nos. 11-23 shows in Table II. Withthe exception of formulation No. 11, the particular bis-phenoxy compound(and the antimony trioxide enhancing agent where indicated) isincorporated into the plastic and solid samples prepared according tothe procedure set forth in Example I.

A virgin nylon 6 plastic material, (Zytel® 211, a product of E. I. duPont de Nemours and Co., Wilmington, Delaware) is utilized as the baseresin in order to prepare 7 formulations (plastic compositions)-- Nos.24-30 shown in Table II. With the exception of formulation No. 24, theparticular bis-phenoxy compound (and the antimony trioxide enhancingagent where indicated) is incorporated into the plastic and solidsamples prepared according to the procedure set forth in Example I.

Regarding Formulation Nos. 31-33 in Table II, a virginpolymethylmethacrylate plastic material, Plexiglas® V (811) acommercially available product of Rohm and Haas Company, Philadelphia,Pennsylvania and being substantially free of additives, is utilized asthe base resin in order to prepare 3 formulations (plasticcompositions). With the exception of formulation No. 31, the particularbis-phenoxy compound (and the antimony trioxide enhancing agent whereindicated) is incorporated into the plastic and solid samples preparedaccording to the procedure set forth in Example I.

Referring to Formulation Nos. 34-37 in Table II, anacrylonitrile-butadiene-styrene (ABS) polymer plastic material, MarbonTP-2098, a product of Marbon Division, Borg-Warner Corporation,Washington, West Virginia, and which is a slight process variation oftheir commercially available "T" grade ABS polymer, is utilized as thebase resin in order to prepare four (4) formulations (plasticcompositions). These formulations, Nos. 34-37, are prepared inaccordance with the procedure described in ASTM D-1897-68.

Portions of the samples of each respective formulation (Nos. 1-37, TableII) prepared respectively according to the above described proceduresare then subjected to two different standard flammability tests, i.e. UL94 and ASTM D-2863-70, i.e. Oxygen Index, O.I.

The results of these flammability tests are shown in Table II.

                  TABLE II                                                        ______________________________________                                        FLAMMABILITY DATA FOR                                                         DIFFERENT PLASTIC COMPOSITIONS                                                CONTAINING BIS-PHENOXY COMPOUNDS WITH AND                                     WITHOUT ENHANCING AGENTS                                                      FORMU- BIS-PHENOXY ENHANCING  OXYGEN                                          LATION COMPOUND    AGENT      INDEX   UL 94                                   NO.    FORMULA %   Sb.sub.2 O.sub.3, %                                                                      %       VALUE                                   ______________________________________                                        Polyacrylonitrile Polymer                                                     1.     --    0         0        22.5    SB                                    2.     III   2         0        23.5    SB                                    3.     III   5         0        23.8    SB                                    4.     III   10        0        24.0    SB                                    5.     III   5         5        25.3    SB                                    6.     III   5         10       25.3    SB                                    7.     II    2         0        23.0    SB                                    8.     II    5         0        23.0    SB                                    9.     II    10        0        24.0    SB                                    10.    II    5         5        25.0    SB                                    Polypropylene Polymer                                                         11.    --    0         0        18.0    Burns                                 12.    III   15        0        20.0    SB                                    13.    III   15        5        22.8    SB                                    14.    III   20        5        26.0    SB                                    15.    III   25        0        24.0    SB                                    16.    III   25        5        26.0    SB                                    17.    II    15        0        19.0    SB                                    18.    II    15        5        22.0    SB                                    19.    II    20        5        25.0    SB                                    20.    II    25        0        23.0    SB                                    21.    II    25        5        25.0    SB                                    22.    III   20        10       25.0    SB                                    23.    II    20        10       24.0    SB                                    Nylon                                                                         24.    --    0         0        23.0    SB                                    25.    III   10        0        23.5    SB                                    26.    III   10        3        24.5    SB                                    27.    III   13        3        27.5    SE-2                                  28.    II    10        0        23.5    SB                                    29.    II    10        3        24.0    SB                                    30.    II    13        3        27.0    SE-2                                  Polymethylmethacrylate Polymer                                                31.    --    0         0        18.0    SB                                    32.    II    15        0        20.5    SB                                    33.    II    15        5        20.5    SB                                    Acrylonitrile-Butadiene-Styrene (ABS) Polymer                                 34.    --    0         0        19.0    HB(SB)                                35.    II    15        0        27.0    HB(SB)                                36.    II    15        5        32.5    V-0(SE-0)                             37.    III   15        5        35.0    V-0(SE-0)                             ______________________________________                                    

Referring to Table II, the bis-phenoxy compound formula II and IIIrelates to the structural formulae heretofor set forth; and the UL 94values are on a graduated scale wherein the highest degree to lowestdegree of flame retardancy is respectively SE-0 (V-0), SE-1 (V-1), SE-2(V-2), SB (HB) and Burns.

The results shown in Table II demonstrate the unexpected and completelyunpredictable results using different polymer systems, in this instancethe unique effectiveness of the plastic composition containing a threecomponent system which consists of the bis-phenoxy compounds, anenhancing agent and acrylonitrilebutadiene-styrene (ABS) polymer ascompared to the use of such bis-phenoxy compound with or without anenhancing agent in a polyacrylonitrile polymer, a polymethylmethacrylatepolymer, a nylon polymer and a polyolefin such as polypropylene polymer,the latter four of which polymers show substantially no increase inflame retardancy via the use of said bis-phenoxy compounds, with orwithout an enhancing agent.

Regarding the use of an enhancing agent in formulation Nos. 5 and 6, theresults obtained therefrom show that there is no increase in flameretardancy. Thus, for example, No. 1 (control) has an UL value of SB andNos. 5 and 6 (which have different enhancing agent levels, 5% versus10%) have also an UL value of SB. In viewing the results of No. 3 (5%-0%) and No. 5 (5%- 5%), it can be seen that even the use of theenhancing agent does not increase flame retardancy in apolyacrylonitrile polymer.

With reference to the polypropylene polymer compositions Nos. 11 thru23, it can readily be seen from the UL 94 values that the incorporationof the particular bis-phenoxy compound therein resulted in substantiallylittle, if any, increase in flame retardancy as compared to the control,considering the experimental accuracy. Even the use of an enhancingagent did not result in an increase in flame retardancy, note No. 12-SBand No. 13-SB. Predicated upon this data, it is thus seen that theincorporation of the bis-phenoxy compounds (with or without an enhancingagent) in a polypropylene results in no flame retardant efficacy.

Specifically referring to the nylon polymer compositions Nos 24-30,formulation No. 24 (the control) had an UL value of SB. In Nos. 25 and28, the use of the particular bis-phenoxy compound results in noincrease in flame retardancy via incorporation of 10% (SB versus SB) ofthe bis-phenoxy compound per se.

Regarding the use of an enhancing agent in formulation Nos. 26, 27, 29and 30, the results obtained therefrom show there is substantiallylittle, if any, increase in flame retardancy. Thus, for example, No. 1(control) has an UL value of SB and Nos. 26 and 29 also have an UL valueof SB. While Nos. 27 and 30 each have an UL value of SE-2, this is notconsidered a significant increase and thus even the use of the enhancingagent does not result in flame retardancy efficacy.

With reference to the polymethylmethacrylate polymer compositions Nos.31, 32 and 33, it can readily be seen from the UL values, i.e. all SB,that the incorporation of the particular bis-phenoxy compound thereinresults in no increase in flame retardancy as compared to the control.Even the use of an enhancing agent did not result in an increase inflame retardancy. Consequently, it can readily be seen that theincorporation of the bis-phenoxy compounds in a polymethylmethacrylateresults in no flame retardant efficacy.

The most unexpected results in flame retardancy were obtained via theincorporation of the particular bis-phenoxy compounds and enhancingagent in an acrylonitrile-butadiene-styrene (ABS) polymer. Referringspecifically to formulation Nos. 34 and 37, the control, formulation No.34, had an UL value of HB(SB). Notwithstanding the incorporation of 15%(No. 35) of the particular bis-phenoxy compound per se in the ABSpolymer, there still results an UL value of SB. Use of the enhancingagent with both bis-phenoxy compounds formulae II and III, informulation Nos. 36 and 37 results in an unexpected UL value change fromSB (No. 35) to SE-0 (No. 36) and SE-0 (No. 37). In view of theseresults, it was quite unexpected that the ABS polymer system, havingincorporated therein the particular bis-phenoxy compounds and enhancingagent would show such superior flame retardant efficacy based on theresults obtained from the performance of the other four (4) polymers,i.e. polyacrylonitrile, polypropylene, nylon and polymethylmethacrylatepolymer systems having the same bis-phenoxy compounds and enhancingagents incorporated therein. Consequently, it can readily be seen thatit is not possible to predict the efficacy and/or functionality of anyhalogen-containing material (which may be suggested as a flameretardant) in any polymeric system until one actually conducts asubstantial research program thereon and ascertains certain propertiesof the "flame retarded" system and its utility.

EXAMPLE VIII

Solid samples of eight different plastic compositions separatelycontaining certain prior art compounds and the herein describedbis-phenoxy compound, both with or without the herein describedenhancing agents, are prepared according to the above described ABSprocedure of Example VII, except that the specimens are injection moldedinstead, rather than compression molded, and are subjected to thefollowing tests in order to ascertain comparative properties of theresultant plastic compositions:

    ______________________________________                                        (1)  Flammability                                                                  (a) Oxygen Index, O.I.                                                                        :    ASTM Test No. D-2863-70                                  (b) UL-94       :    UL-94 Procedure described                                                     herein and dated February 1,                                                  1974.                                               (2)  Light Stability                                                               (Weather Ometer)                                                                              :    Procedure described herein                               (a) Visual rank      and in Example V, except                                   (1 is the highest) that the light source is the                             (b) Gardner Colorimeter                                                                            Xenon arc rather than a                                    ("Δ E" Values)                                                                             carbon arc.                                         (3)  Initial Color   :    Visual color observation                                                      immediately after injection                                                   molding.                                            (4)  Visual Migration                                                                              :    Visual observation of sur-                                                    face haze presence.                                 (5)  TGA and Isotherm                                                                              :    Procedure described in                                                        Example VI.                                         (6)  Melt Flow       :    ASTM Test No. 1238-70.                              (7)  Notched Izod Impact                                                                           :    ASTM Test D256-72a; and                             (8)  Heat Distortion                                                               Temperature (HDT)                                                                             :    ASTM Test No. D648-72.                              ______________________________________                                    

Regarding item (2) above, i.e. light stability, the results obtained viathe "Visual" rank include any color changes which occurred in the moldedmaterials tested from a combination of processing and exposure to thexenon arc.

Each of the aforementioned Tests are standard tests in the art and areutilized collectively in order to ascertain the efficacy of a polymericsystem as an overall flame retardant composition for commercialapplication. All of these tests are to be considered as incorporatedherein by reference.

The different polymers utilized along with trade names and correspondingsuppliers are listed below.

    ______________________________________                                        Polymer       Trademark      Supplier                                         ______________________________________                                        ABS           Cycolac T-2098 Borg-Warner                                      Polystyrene   Bakelite TMDE-6500                                                                           Union Carbide                                     (high impact) HIPS                                                           Polycarbonate Lexan 141      General Electric                                 Nylon 6       Zytel 211      DuPont                                           Polypropylene Profax 6523    Hercules                                         Terephthalate polyester                                                                     Valox 310      General Electric                                 Polyphenylene oxide,                                                                        Noryl 731      General Electric                                  modified (PPO)                                                               Polyethylene, Bakelite DPD-3900                                                                            Union Carbide                                     Low Density (LDPE)                                                           ______________________________________                                    

The concentration of the additives (i.e. prior art compounds--designated PAC--or certain bis-phenoxy compounds-- designated BPC--withor without an enhancing agent-- designated EA--and the respective TableNos. listing the pertinent data are shown below. The Table numbers areshown in parenthesis.

    ______________________________________                                                  PAC or                                                              Polymer   BPC/EA----Sb.sub.2 O.sub.3 %                                                                  PAC or BPC ONLY                                     ______________________________________                                        ABS       15/5 (III)      20/0 (IV) +30/0 (V)                                 HIPS      12/4 (VI)       16/0 (VII) + 30/0 (VIII)                            Polycarbonate                                                                           3/1 (IX)                                                            Nylon     12/4 (X)                                                            Polypropylene                                                                           12/4 (XI)                                                           Polyester 12/4 (XII)      16/0 (XIII)                                         PPO       9/3 (XIV)                                                           PPO       9/3 Pigmented TiO.sub.2 (XV)                                        LDPE      20/5 (XVI)                                                          ______________________________________                                    

All percentages (%) shown are on a weight basis, based on the totalweight of the plastic composition.

The identification of the prior art compounds (PAC) listed as A,B,C,D,Eand F in the Tables are shown below:

    ______________________________________                                        PAC                                                                           (Letter)                                                                              FORMULA                                                               ______________________________________                                        A       C.sub.6 Cl.sub.5 C.sub.6 Cl.sub.5                                             (decachlorobiphenyl)                                                  B       C.sub.6 Br.sub.5 OC.sub.6 Br.sub.5                                            Bis-(pentabromophenyl)ether                                           C       C.sub.6 Br.sub.6                                                              Hexabromobenzene                                                      D       C.sub.6 Br.sub.5 CH.sub.2 Br                                                  Pentabromobenzyl bromide                                              E       C.sub.6 H.sub.2 Br.sub.2 (OCH.sub.3)C(CH.sub.3).sub.2 C.sub.6                 H.sub.2 Br.sub.2 (OCH.sub.3)                                                  Bis-2,2-(3,5-dibromo-4-methoxyphenyl)propane                          F       C.sub.6 H.sub.2 Br.sub.3 OCH.sub.2 CBr=CBrCH.sub.2 OC.sub.6                   H.sub.2 Br.sub.3                                                              Trans 1,4-Bis(2,4,6-tribromophenoxy-2,3-dibromo-2-                            butene                                                                ______________________________________                                    

The certain bis-phenoxy compounds (BCP) listed in the Tables underPresent Invention, as II, III, VI, etc. correspond to those compoundslisted on pages 11 and 12 of this specification.

The control (base resin) is the particular designated polymer withoutthe PAC, BPC or EA.

The results of this comparative testing are set forth in Tables IIIthrough XVI.

                                      Table III                                   __________________________________________________________________________                Control                                                                           Prior Art              Present Invention                      Resin ABS   (Base                                                                             Compounds              Compounds                              Additive 15/5                                                                             Resin)                                                                            A   B   C   D  E   F   II  III VI  IV  VIII                                                                              IX                 __________________________________________________________________________    Oxygen Index, %                                                               at 73° F.                                                                          18.5                                                                              21.5                                                                              28.0                                                                              27.5                                                                              35.0                                                                             26.0                                                                              34.5                                                                              30.5                                                                              28.0                                                                              30.5                                                                              31.0                                                                              36.0                                                                              30.0               UL-94 1/8" thickness                                                                      HB  HB  V-O V-O V-O                                                                              HB  V-O V-O V-O V-O V-O V-O V-O                Xenon Arc                                                                     Weather-Ometer                                                                            5   6   12  10  13 3   11  7   8   9   2   1   4                  (Ranked)                                                                      Injection Molded                                                              Initial color                                                                             White                                                                             Off-                                                                              Off-                                                                              Off-                                                                              Tan                                                                              Off-                                                                              Light                                                                             White                                                                             White                                                                             White                                                                             White                                                                             White                                                                             White                              White                                                                             White                                                                             White  White                                                                             Cream                                      Visual  Initial None                                                                              None                                                                              None                                                                              None                                                                             None                                                                              None                                                                              None                                                                              None                                                                              None                           Migration                                                                             7 days  None                                                                              None                                                                              None                                                                              None                                                                             None                                                                              None                                                                              None                                                                              None                                                                              None                                           266     249                                                   TGA 5% wt. loss ° C.                                                               329 48 hr.                                                                            307 48 hr.                                                                            261                                                                              271 274 285 290 310                            Isotherm 72 hr., 150° C.                                                           1.83                                                                              0.415   0.727      1.27                                                                              1.11                                   Melt Flow g/10 min.                                                                       3.2 3.6 4.0 4.5 8.3                                                                              9.9 4.9 8.2 6.7 3.4                            Conditions "G"                                                                200° C., 5000 g                                                        Notched Izod Impact                                                           ft. lbs/in 1/2 × 1/8                                                                3.27                                                                              1.62                                                                              1.40                                                                              1.19                                                                              1.56                                                                             1.62                                                                              1.23                                                                              1.93                                                                              2.12                                                                              1.19                                                                              2.08                                                                              1.92                                                                              1.32               Heat Deflection Temp.                                                         °F. at 264 psi                                                                     192 189 187 190 184                                                                              171 185 180 176 190                            Annealed at 180° F.                                                    Concentrate                                                                   compounding     400 400 400 400                                                                              400 400 450 350 400 400 400 400                Temperature, °F.                                                       Injection Molding                                                             Temperature, ° F.                                                                  450 450 450 450 450                                                                              450 430 450 450 450 450 450 450                Gardner Color Value,                                                          ΔE    6.5 3.9 20.1                                                                              11.9                                                                              12.7                                                                             4.6 8.6 6.7 7.9 7.3 0.9 4.1 1.1                After 100 hours,                                                              Xenon Arc                                                                     __________________________________________________________________________

                                      Table IV                                    __________________________________________________________________________                Control                                                                           Prior Art               Present Invention                     Resin ABS   (Base                                                                             Compounds               Compounds                             Additive 20/0                                                                             Resin)                                                                            A   B   C   D   E   F   II  III IV                                                                              VI  VIII                                                                             IX                   __________________________________________________________________________    Oxygen Index, %                                                               at 73° F.                                                                          18.5                                                                              20.5                                                                              24.5                                                                              24.0                                                                              27.0                                                                              22.5    24.0                                                                              22.5  27.0                        UL-94 1/8" thickness                                                                      HB  HB  HB  V-O V-O HB      HB  HB    V-O                         Xenon Arc                                                                     Weather-Ometer                                                                            1   5   7   6   8   1       2   3     4                           (Ranked)                                                                      Injection Molded                                                                          White                                                                             Off-                                                                              Off-                                                                              Off-                                                                              Tan White                                                                             De- White                                                                             White Off-                        Initial Color   White                                                                             White                                                                             White       com-          White                                                           posed                                     Visual  Initial None                                                                              None                                                                              None                                                                              None                                                                              None    None                                                                              None  None                        Migration                                                                             7 days                                                                TGA 5% wt. loss ° C.                                                   Isotherm 72 hr., 150° C.                                               Melt Flow g/10 min. -Conditions "G"                                           200° C., 5000 g                                                        Notched Izod Impact                                                           ft. lbs/in. 1/2 × 1/8                                                               3.27                                                                              1.40                                                                              1.43                                                                              1.17                                                                              1.15                                                                              1.97    3.27                                                                              4.18  1.45                        Heat Deflection Temp.                                                         °F. at 264 psi,                                                        Annealed at 180° F.                                                    Concentrate                                                                   Compounding                                                                   Temperature, °F.                                                                       400 400 400 400 400 400 400 400   400                         Injection Molding                                                             Temperature, °F.                                                                   450 450 450 450 420 450     450 450   450                         Gardner Color Value,                                                          Δ E                                                                     After 100 hours,                                                                          6.5 8.0 19.8                                                                              11.1                                                                              8.5 4.6     4.4 5.2   5.6                         Xenon Arc                                                                     __________________________________________________________________________

                                      Table V                                     __________________________________________________________________________                Control                                                                           Prior Art              Present Invention                      Resin ABS   (Base                                                                             Compounds              Compounds                              Additive 30/0                                                                             Resin)                                                                            A   B   C   D   E   F  II  III IV                                                                              VI  VIII                                                                             IX                    __________________________________________________________________________    Oxygen Index, %                                                                           18.5                                                                              21.5                                                                              30.0                                                                              30.0                                                                              32.0                                                                              27.0                                                                              30.0                                                                             33.5                                                                              34.0  35.5                         at 73° F.                                                              UL-94 1/8" thickness                                                                      HB  HB  V-O V-O V-O V-O V-O                                                                              V-O V-O   V-O                          Xenon Arc                                                                     Weather-Ometer                                                                            3   5   10  8   11  1   7  4   2     6                            (Ranked)                                                                                      Egg Egg Egg                      Egg                          Injection Molded                                                                          White                                                                             Shell                                                                             Shell                                                                             Shell                                                                             Light                                                                             White                                                                             Light                                                                            White                                                                             White Shell                        Initial Color   White                                                                             White                                                                             White                                                                             Brown   Tan          White                        Visual  Initial                                                               Migration                                                                             7 days                                                                TGA 5% wt. loss ° C.                                                   Isotherm 72 hr., 150° C.                                               Melt Flow g/10 min.                                                           Conditions "G"                                                                200° C., 5,000g                                                        Notched Izod Impact                                                           ft. lbs/in. 1/2 × 1/8                                                               3.27                                                                              1.06                                                                              1.08                                                                              1.09                                                                              1.50                                                                              1.42                                                                              1.19                                                                             2.49                                                                              3.65  1.13                         Heat Deflection Temp.                                                         ° F. at 264 psi,                                                       Annealed at 180° F.                                                    Concentrate --  440 440 440 392 392 356                                                                              440 400   440                          Compounding                                                                   Temperature, ° F.                                                      Injection Molding                                                             Temperature, ° F.                                                                  450 450 450 450 400 430 400                                                                              450 450   450                          Gardner Color Value,                                                                      6.5 1.4 9.0 2.6 6.5 1.6 2.5                                                                              2.6 1.2   0.8                          ΔE                                                                      After 100 hours,                                                              Xenon Arc                                                                     __________________________________________________________________________

                                      Table VI                                    __________________________________________________________________________                Control                                                                           Prior Art               Present Invention                     Resin HIPS  (Base                                                                             Compounds               Compounds                             Additive 12/4                                                                             Resin)                                                                            A   B   C   D   E   F   II  III IV VI  VIII                                                                              IX                 __________________________________________________________________________    Oxygen Index, %                                                               at 73° F.                                                                          18.5                                                                              20.0                                                                              26.0                                                                              23.5                                                                              27.0                                                                              23.0                                                                              25.0                                                                              21.0                                                                              23.0   25.5                                                                              26.5                                                                              26.0               UL-94 1/8" thickness                                                                      HB  HB  V-0 V-0 V-0 HB  V-2 HB  HB     V-0 V-0 HB                 Xenon Arc                                                                     Weather-Ometer                                                                            1   5   11  10  12  3   9   4   6      8   2   7                  (Ranked)                                                                      Injection Molded                                                                          White                                                                             Light                                                                             Cream                                                                             Grey                                                                              Light                                                                             White                                                                             Tan Off-                                                                              Off-   Off-                                                                              Off-                                                                              Off-               Initial Color   Cream   Cream                                                                             Cream       White                                                                             White  White                                                                             White                                                                             White                                  per-                                                                              per-    per-                                                              haps                                                                              haps    haps                                          Visual  Initial                                                                           None                                                                              None                                                                              Slight                                                                            Slight                                                                            None                                                                              Slight                                                                            None                                                                              None                                                                              None   None                       Migration                                                                             7 days                                                                            None                                                                              None                                                                              None                                                                              None                                                                              None                                                                              None                                                                              None                                                                              None                                                                              None   None                       TGA 5% wt. loss ° C.                                                               322 270 325 263 254 279 277 304 305    325                        Isotherm 48 hr., 150° C.                                                           0.582                                                                         0.410                                                                             1.44                                                                              0.301                                                                             1.04                                                                              3.12                                                                              1.17                                                                              0.885                                                                             0.940                                                                             0.758  0.22                       Melt Flow g/10 min.                                                           Conditions "G"                                                                            6.2 11.0                                                                              8.8 10.4                                                                              13.3                                                                              11.1                                                                              15.8                                                                              10.7                                                                              13.8   7.1                        200° C., 5000g                                                         Notched Izod Impact                                                           ft.lbs/in. 1/2 × 1/8                                                                2.12                                                                              1.61                                                                              1.71                                                                              1.66                                                                              1.65                                                                              1.64                                                                              1.25                                                                              1.76                                                                              1.63   1.69                                                                              1.73                                                                              1.72               Heat Deflection Temp.                                                         ° F. at 264 psi,                                                                   182 171 180 171 165 157 172 172 157    177                        Annealed at 180° F.                                                    Concentrate --  400 400 400 400 400 400 450 400    400 400 400                Compounding                                                                   Temperature, ° F.                                                      Injection Molding                                                                         450 450 450 450 450 430 430 450 430    450 450 450                Temperature, ° F.                                                      Gardner Color Value,                                                          ΔE                                                                      After 24 hours,                                                                           0.7 17.6                                                                              33.6                                                                              23.9                                                                              34.3                                                                              7.0 11.0                                                                              11.0                                                                              20.9   14.4                                                                              4.3 16.3               Xenon Arc                                                                     __________________________________________________________________________

                                      Table VII                                   __________________________________________________________________________                Control                                                                           Prior Art               Present Invention                     Resin HIPS  (Base                                                                             Compounds               Compound                              Additive 16/0                                                                             Resin)                                                                            A   B   C   D   E   F   II  III IV                                                                              VI  VIII                                                                             IX                   __________________________________________________________________________    Oxygen Index, %                                                               at 73° F.                                                                          18.5                                                                              18.5                                                                              22.0                                                                              22.0    21.5    21.0                                                                              21.5  22.0                        UL-94 1/8" thickness                                                                      HB  HB  V-2 HB      HB      HB  HB    HB                          Xenon Arc                                                                     Weather-Ometer                                                                            1   2   9   7       5       3   6     4                           (Ranked)                                                                      Injection Molded                                                                          White                                                                             Off-                                                                              Cream                                                                             Cream                                                                             De- White                                                                             De- Off-                                                                              White Cream                       Initial Color   White       com-    com-                                                                              White                                                             po-     po-                                       Visual  Initial None                                                                              None                                                                              None                                                                              si- None                                                                              si- None                                                                              None  None                        Migration                                                                             7 days  None                                                                              None                                                                              None                                                                              tion                                                                              None                                                                              tion                                                                              None                                                                              None  None                        TGA 5% wt. loss ° C.                                                   Isotherm 72 hr. 150° C.                                                Melt Flow g/10 min.                                                           Conditions "G"                                                                200 C 5000g                                                                   Notched Izod Impact                                                           ft.lbs/in. 12 × 1/8                                                                 2.12                                                                              1.64                                                                              1.69                                                                              1.58    1.59    1.62                                                                              1.60  1.66                        Heat Deflection Temp.                                                         ° F. at 264 psi,                                                       Annealed at 180° F.                                                    Concentrate                                                                   Compounding                                                                   Temperature, ° F.                                                                      400 400 400     400     400 400   400                         Injection Molding                                                                         450 450 450 450     450     450 450   450                         Temperature, ° F.                                                      Gardner Color Value,                                                          Δ E                                                                     After 24 hours,                                                                           0.7 19.4                                                                              25.9                                                                              23.2    21.7    34.0                                                                              30.5  17.8                        Xenon Arc                                                                     __________________________________________________________________________

                                      Table VIII                                  __________________________________________________________________________                Control                                                                           Prior Art               Present Invention                     Resin HIPS  (Base                                                                             Compounds               Compounds                             Additive 30/0                                                                             Resin)                                                                            A   B   C   D   E   F   II  III IV                                                                              VI  VIII                                                                             IX                   __________________________________________________________________________    Oxygen Index, %                                                               at 73° F.                                                                          18.5                                                                              21.0                                                                              25.5                                                                              25.5                                                                              30.0                                                                              25.0                                                                              27.0                                                                              27.0                                                                              25.0  32.0                        UL-94 1/8" thickness                                                                      HB  HB  V-0 V-0 V-O V-0 V-0 V-0 V-0   V-0                         Xenon Arc                                                                     Weather-Ometer                                                                            1   5   10  7   9   2   8   4   6     3                           (Ranked)                                                                      Injection Molded                                                                          Trans-                                                                            Biege                                                                             Light                                                                             Grey                                                                              Brown                                                                             Light                                                                             Tan Off-                                                                              Off-  Light                       Initial Color                                                                             luscent Grey        Tan     White                                                                             White Biege                       Visual  Initial                                                               Migration                                                                             7 days                                                                TGA 5% wt. loss ° C.                                                   Isotherm 72 hr., 150° C.                                               Melt Flow g/10 min.                                                           Conditions "G"                                                                200° C., 5000g                                                         Notched Izod Impact                               R 1.08                      ft.lbs/in. 1/2 × 1/8                                                                2.12                                                                              1.10                                                                              1.21                                                                              1.43                                                                              1.45                                                                              1.27                                                                              1.11                                                                              1.39                                                                              1.35  1.10                        Heat Deflection Temp.                                                         °F. 264 psi,                                                           Annealed at 180° F.                                                    Concentrate                                                                   Compounding                                                                   Temperature, ° F.                                                                      450 450 430 356 392 356 450 400   450                         Injection Molding                                                             Temperature, ° F.                                                                  450 430 430 410 380 400 380 430 410   430                         Gardner Color Value,                                                          Δ E                                                                     After 24 hours,                                                                           0.7 22.4                                                                              29.7                                                                              15.8                                                                              10.4                                                                              5.1 12.1                                                                              17.2                                                                              24.9  6.8                         Xenon Arc                                                                     __________________________________________________________________________

                                      Table IX                                    __________________________________________________________________________                 Control                                                                            Prior Art                Present Invention                  Resin Polycarbonate                                                                        (Base                                                                             Compounds                 Compounds                          Additive 3/1 Resin)                                                                             A    B   C   D   E   F    II  III IV                                                                               VI VIII                                                                             IX               __________________________________________________________________________    Oxygen Index, %                                                               at 73° F.                                                                           25.0                                                                              36.5 41.5                                                                              39.5                                                                              39.5                                                                              37.0     36.5 37.5  40.0                    UL-94 1/8" thickness                                                                        HB  V-2  V-0                                                                              V-2 V-2 V-0      V-0  V-0   V-0                     Xenon Arc                             Decompo-                                Weather-Ometer (Ranked)                                                                     1   5    10  8   9   3  sition                                                                              2    4     7                      Injection Molded                                                                           Clear                                                                             Light                                                                              Light                                                                             Light                                                                             Cream                                                                             Light    Off- Cream Off-                    Initial Color    Cream                                                                              Cream                                                                             Cream   Cream    White      White                                    Perhaps                   Perhaps                            Visual Initial   Slight                                                                             None                                                                              None                                                                              None                                                                              None     Slight                                                                             None  None                    Migration 7days  None None                                                                              None                                                                              None                                                                              None     None None  None                    TGA 5% wt. loss ° C.                                                                427 381  379 375 366 378      398  374   388                     Isotherm 24 hr. 200° C.                                                             0.394                                                                             1.20 0.529                                                                             1.78                                                                              1.18                                                                              1.12     0.664                                                                              0.655 0.326                   Melt Flow g/10 min.                                                           Conditions "G" 275° C.,                                                              9.8                                                                              11.8 12.7                                                                              18.8                                                                              17.2                                                                              16.8     8.8  17.4  11.4                    1,200g                                                                        Notched Izod Impact                                                           ft. lbs/in. 1/2 × 1/8                                                                16.50                                                                             6.64 8.54                                                                              2.73                                                                              1.02                                                                              3.16     16.98                                                                              7.25  9.41                    Heat Deflection Temp.                                                         ° F. at 264 psi,                                                                     279                                                                              265  267 260 259 262      265  259   268                     Annealed at 180° F.                                                                                          Degrad-                                 Concentrate Compounding                                                                        500  480 480 500 500 ed at                                                                              500  500   500                     Temperature, ° F.              500                                     Injection Molding                                                             Temperature, ° F.                                                                    520                                                                              520  520 520 520 520      520  520   520                     Gardner Color Value, ΔE                                                 After 48 hours, Xenon Arc                                                                   1.1                                                                              4.7  22.2                                                                              10.1                                                                              6.7 3.8      3.6  3.6   9.6                     __________________________________________________________________________

                                      Table X                                     __________________________________________________________________________                 Control                                                                             Prior Art             Present Invention                    Resin Nylon 6                                                                              (Base                                                                              Compounds             Compounds                             Additive 12/4                                                                              Resin)                                                                              A   B   C   D  E   F  II  III  IV                                                                               VI VIII                                                                              IX                __________________________________________________________________________    Oxygen Index, %                                                               at 73° F.                                                                           21.5 26.0                                                                              28.5                                                                              29.0          24.5        27.5                                                                  Molding                                                         Did    Did    Problems                          UL-94 1/8" thickness                                                                       HB   V-2 V-0 V-2 Not                                                                              Decom-                                                                            Not                                                                              V-2 Decom-  V-0                                                     Mold                                                                             posed                                                                             Mold   posed                             Xenon Arc                                                                     Weather-Ometer (Ranked)                                                       Injection Molded                                                                           Natural                    Off-                                  Initial Color                                                                              (white)                                                                            Cream                                                                             Cream                                                                             Cream         White       Cream                     Visual Initial    None                                                                              None                                                                              None          None        None                      Migration 7 days  None                                                                              None                                                                              None          None        None                      TGA 5% wt. loss ° C.                                                                237  219 219 204           214         220                       Isotherm 48 hr. 150° C.                                                             5.67 4.70                                                                              4.60                                                                              4.76          4.49        4.97                      Melt Flow g/10 min.                                                           Conditions "G" 100° C                                                  5000g                                                                         Notched Izod Impact                                                           ft.lbs./in. 1/2 × 1/8                                                                3.09 1.85                                                                              1.66                                                                              1.60          2.54        2.20                      Heat Deflection Temp.                                                         ° F. at 264 psi,                                                                    125  137 133 135           132         136                       Annealed at 100° F.                                                    Concentrate Compounding                                                       Temperaure, ° F.                                                                         440 440 440    440    440         440                       Injection Molding                                                             Temperature, ° F.                                                                   480  480 480 480    450    480         480                       Gardner Color Value, ΔE                                                 After 100 hours, Xenon Arc                                                                 0.9  2.0 3.7 2.5           2.4         7.9                       __________________________________________________________________________

                                      Table XI                                    __________________________________________________________________________               Control                                                                           Prior Art                  Present Invention                   Resin Polypropylene                                                                      (Base                                                                             Compounds                  Compounds                           Additive 12/4                                                                            Resin)                                                                             A    B    C   D   E    F   II  III  IV                                                                               VI VIII                                                                             IX               __________________________________________________________________________    Oxygen Index, %                                                               at 73° F.                                                                         17.5                                                                              21.0 24.0 25.0                                                                              24.0                                                                              20.5 31.5                                                                              21.5 23.5   23.0                    UL-94 1/8" HB  HB   V-2  HB  V-2 HB   V-0 HB   V-2    HB                      thickness                                                                     Xenon Arc                                                                     Weather-Ometer                                                                           1   4    11   9   10  5    8   3    2      6                       (Ranked)                                                                      Injection Molded                                                                         Clear                                                                             Off- Off- Cream                                                                             Cream                                                                             Off- Cream                                                                             Off- Off-   Off-                    Initial Color  White                                                                              White        White    White                                                                              White  White                                  Perhaps                                                                            Perhaps  Perhaps  Perhaps                                                                           Perhaps                             VisualInitial  Slight                                                                             Slight                                                                             None                                                                              None                                                                              Slight   Slight                                                                             Slight None                    Migration 7 days                                                                             Perhaps                                                                            None None                                                                              None                                                                              None     Perhaps                                                                            Perhaps                                                                              None                                   Slight                     Slight                                                                             Slight                         TGA 5% wt. loss ° C.                                                              272 264  274  256 252 260  269 275  273    276                     Isotherm   0.00                                                               48 hr. 150° C.                                                                    0.20                                                                              0.937                                                                              0.493                                                                              3.7 13.6                                                                              2.14 0.756                                                                             0.607                                                                              0.873  0.33                    Melt Flow g/10 min.                                                           Conditions "L,"                                                                          5.2 9.3  6.8  9.8 9.3 9.9  17.7                                                                              10.4 8.9    6.4                     230° C.,2,160g                                                         Notched Izod Impact                                                           ft.lbs/in. 1/2 × 1/8                                                               1.22                                                                              1.19 1.21 1.12                                                                              1.16                                                                              1.13 1.10                                                                              0.96 1.07   1.20                    Heat Deflection                                                               Temp. ° F. at 66 psi,                                                             246 253  240  276 240 235  267 267  257    277                     Annealed at 194° F.                                                    Concentrate                                                                   Compounding    400  420  400 360 450  420 400  400    400                     Temperature, ° F.                                                      Injection Molding                                                                        440 440  440  400 440 440  400 440  440    440                     Temperature, ° F.                                                      Gardner Color                                                                 Value, Δ E After                                                        48 hours,  0.5 5.3  12.8 10.0                                                                              8.8 5.6  7.3 2.7  2.7    4.8                     Xenon Arc                                                                     __________________________________________________________________________

                                      Table XII                                   __________________________________________________________________________                 Control                                                                            Prior Art                 Present Invention                 Resin Polyester                                                                            (Base                                                                              Compounds                 Compounds                         Additive 12/4                                                                              Resin)                                                                              A    B   C   D   E   F   II  III IV                                                                              VI  VIII                                                                             IX               __________________________________________________________________________    Oxygen Index, %                                                               at 73° F.                                                                           22.0 28.0 32.0                                                                              32.0                                                                              32.0                                                                              26.0     30.0                                                                              29.0  32.0                    UL-94 1/8" thickness                                                                       HB   V-2  V-0 V-0 V-0 V-2      V-2 V-2   V-0                     Xenon Arc                              Decom-                                 Weather-Ometer (Ranked)                                                                    1    5    9   7   8       position                                                                           3   2     4                       Injection Mold3d                                                                           White                                                                              Off- Off-                                                                              Off-                                                                              Cream                                                                             Cream    White                                                                             White Cream                   Initial Color     White                                                                              White                                                                             White                                              Visual Initial    None None                                                                              None                                                                              None                                                                              None     None                                                                              None  None                    Migration 7 days  None None                                                                              None                                                                              None                                                                              None     None                                                                              None  None                    TGA 5% wt. loss ° C.                                                                369  281  346 266 292 305      311 330   351                     Isotherm 24 hr. 200° C.                                                             0.576                                                                              1.97 0.115                                                                             3.66                                                                              4.67                                                                              2.89     1.99                                                                              0.606 0.446                                0.489                                                            Melt Flow g/10 min.                                                                        15.0 11.5 12.8                                                                              10.8                                                                              22.0                                                                              16.5     6.5 25.8  11.3                    Conditions "H", 230° C.,                                               1,260g                                                                        Notched Izod Impact                                                                        1.51 1.04 1.00                                                                              1.07                                                                              0.96                                                                              1.12     1.19                                                                              1.33  0.90                    ft. lbs/in. 1/2 × 1/8                                                   Heat Deflection Temp.                                                                      123  122  127 127 121 123      117 122   139                     ° F. at 264 psi                                                        Annealed at 100° F.                                                    Concentrate Compounding                                                                         450  450 450 450 450      450 450   450                     Temperature, ° F.                                                      Injecton Molding                                                                           470  460  460 460 470 470      460 470   460                     Temperature, ° F.                                                      Gardner Color Value, Δ E                                                After 24 hours, Xenon Arc                                                                  1.9  7.8  22.6                                                                              7.3 8.5 1.9      3.4 3.1   4.2                     __________________________________________________________________________

                                      Table XIII                                  __________________________________________________________________________                   Control                                                                            Prior Art       Present Invention                         Resin Polyester                                                                              (Base                                                                              Compounds       Compounds                                 Additive 16/0  Resin)                                                                              A   B  C  D                                                                               E                                                                               F                                                                              II  III IV                                                                              VI  VIII                                                                             IX                       __________________________________________________________________________    Oxygen Index, %                                                               at 73° F.                                                                             22.0 28.0                                                                              23.0                                                                             28.5     27.5                                                                              27.5  27.5                            UL-94 1/8" thickness                                                                         HB   V-2 V-2                                                                              V-2      V-2 V-2   V-2                             Xenon Arc                                                                     Weather-Ometer (Ranked)                                                       Injecton Molded                                                                              White                                                                              Off-                                                                              Light                                                                            Light    Off-                                                                              White White                           Initial Color       White                                                                             Tan                                                                              Grey     White                                     Visual Initial                                                                Migration 7 days                                                              TGA 5% wt. loss ° C.                                                   Isotherm 24 hr., 200° C.                                               Melt Flow g/10 min.                                                           Conditions "H",230° C.,                                                1,260g                                                                        Notched Izod Impact                                                           ft. lbs/in. 1/2 × 1/8                                                                  1.51 0.93                                                                              1.32                                                                             1.13     1.19                                                                              1.33  1.13                            Heat Deflection Temp.                                                         ° F. at 264 psi,                                                       Annealed at 100° F.                                                    Concentrate Compounding                                                       Temperature, ° F.                                                                          450 450                                                                              450      470 470   450                             Injection Molding                                                             Temperature, ° F.                                                                     470  460 460                                                                              460      460 460   460                             Gardner Color Value, Δ E                                                After 24 hours, Xenon Arc                                                     __________________________________________________________________________

                                      Table XIV                                   __________________________________________________________________________                   Control                                                                           Prior Art                Present Invention                 Resin PPO      (Base                                                                             Compounds                Compounds                         Additive 9/3   Resin)                                                                             A   B   C   D   E    F   II III IV                                                                              VI  VIII                                                                             IX               __________________________________________________________________________    Oxygen Index, %                                                               at 73° F.                                                                             26.5                                                                              25.0                                                                              30.0                                                                              28.0                                                                              31.0                                                                              27.0 30.0                                                                              27.5                                                                              29.0  27.0                    UL-94 1/8" thickness                                                                         V-1 V-1 V-0 V-0 V-0 V-0  V-0 V-0 V-0   V-0                     Xenon Arc                                                                     Weather-Ometer (Ranked)                                                       Injection Molded                                                              Initial Color  Brown                                                                             Brown                                                                             Brown                                                                             Brown                                                                             Brown                                                                             Brown                                                                              Brown                                                                             Brown                                                                             Brown Brown                                                      Perhaps                                    Visual Initial     None                                                                              None                                                                              None                                                                              None                                                                              Slight                                                                             None                                                                              None                                                                              NOne  None                    Migration 7 days   None                                                                              None                                                                              None                                                                              None                                                                              None None                                                                              None                                                                              None  None                    TGA 5% wt. loss ° C.                                                                  281 249 294 244 243 262  261 277 276   279                     Isotherm 24 hr. 200° C.                                                               1.87                                                                              4.07                                                                              2.21                                                                              5.00                                                                              3.88                                                                              3.19 5.40                                                                              3.08                                                                              3.19  2.35                    Melt Flow g/10 min.                                                                          1.4 3.3 2.1 2.6     3.7      3.8 3.0   1.9                     Conditions                                                                    Notched Izod Impact                                                                          4.02                                                                              2.39                                                                              2.44                                                                              2.44                                                                              1.94                                                                              2.97 1.77                                                                              2.50                                                                              2.60  1.89                    ft.lbs/in. 1/2 × 1/8                                                    Heat Deflection Temp.                                                         ° F. at 264 psi,                                                                      209 196 205 200 200 177  194 193 190   203                     Annealed at 200° F.                                                    Concentrate Compounding                                                                          450 450 450 450 450  450 450 450   450                     Temperature, ° F.                                                      Injection Molding                                                                            450 450 450 450 450 450  450 450 450   450                     Temperature, ° F.                                                      Gardner Color Value, Δ E                                                After --hours, Xenon Arc                                                      __________________________________________________________________________

                                      Table XV                                    __________________________________________________________________________                   Control                                                                           Prior Art             Present Invention                    Resin PPO      (Base                                                                             Compounds             Compounds                            Additive 9/3 (Pigmented)                                                                     Resin)                                                                            A  B   C   D   E   F   II III IV VI  VIII                                                                              IX                __________________________________________________________________________    Oxygen Index, %                                                               at 73° F.                                                                             25.0  32.0                                                                              31.0                                                                              33.5                                                                              26.5                                                                              32.5                                                                              28.0                                                                              28.5   30.0                      UL-94 1/8"thickness                                                                          HB    V-O V-O V-O V-O V-O V-O V-O    V-O                       Xenon Arc                                                                     Weather-Ometer (Ranked)                                                                       1     9   6   8   1   7   3   2      4                        Injection Molded                                                                             Light Light                                                                             Light   Light                                                                             Dark                                                                              Light                                                                             Light  Light                     Initial Color  Tan   Tan Tan Tan Tan Tan Tan Tan    Tan                       Visual Initial None  None                                                                              None                                                                              None                                                                              None                                                                              None                                                                              None                                                                              None   None                      Migration 7 days                                                                             None  None                                                                              None                                                                              None                                                                              None                                                                              None                                                                              None                                                                              None   None                      TGA 5% wt. loss ° C.                                                                  389   335 284 291 311 275 338 324    337                       Isotherm 24 hr. 200° C.                                                               0.299 0.420                                                                             0.893                                                                             0.865                                                                             0.587                                                                             1.02                                                                              0.5556                                                                            0.272  0.476                     Melt Flow g/10 min.                                                           Conditions                                                                    Notched Izod Impact                                                                          3.24  2.14                                                                              2.00                                                                              1.19                                                                              2.02                                                                              1.40                                                                              2.16                                                                              2.18   1.82                      ft. lbs/iin. 1/2 ×1/8                                                   Heat Deflection Temp.                                                         ° F. at 264 psi,                                                                      246   233 226 227 210 221 210 207    237                       Annealed at 200° F.                                                    Concentrate Compounding                                                                      450   450 450 450 450 450 450 450    450                       Temperature, ° F.                                                      Injection Molding                                                             Temperature, ° F.                                                                     460   460 460 460 460 460 460 460    460                       Gardner Color Value, Δ E                                                After 48 hours, Xenon Arc                                                                    3.6   13.3                                                                              9.2 9.0 5.9 14.8                                                                              5.3 4.9    6.9                       __________________________________________________________________________

                                      Table XVI                                   __________________________________________________________________________                   Control                                                                           Prior Art              Present Invention                   Resin LDPE     (Base                                                                             Compounds              Compounds                           Additive 20/5  Resin)                                                                            A  B    C   D   E   F   II III IV VI  VIII                                                                             IX                __________________________________________________________________________    Oxygen Index, %                                                               at 73° F.                                                                             18.0  28.0 29.0                                                                              27.0                                                                              26.5                                                                              26.5                                                                              26.0                                                                              28.0   26.5   25.5              UL-94 1/8" thickness                                                                          HB   V-0  V-2 V-2 V-2 V-2 V-2 V-0    V-0    V-2               Xenon Arc                                                                     Weather-Ometer (Ranked)                                                       Injection Molded                                                                             Natural                                                                             Off- Light                                                                             Off-                                                                              White                                                                             Cream                                                                             White                                                                             White  White                    Initial Color        White                                                                              Grey                                                                              White                                           Visual Initial       None Yes Yes None                                                                              None                                                                              None                                                                              Yes    None                     Migration 7 days     None Yes Yes None                                                                              Yes None                                                                              Yes    None                     TGA 5% wt. loss ° C.                                                                  302   330  248 248 265 267 305 308    332                      ISotherm 48 hr. 150° C.                                                                0     0   1.84                                                                              2.42                                                                              0.78                                                                              0.66                                                                              0.26                                                                              0.41   0.16                     Melt Flow g/10 min.                                                           Conditions "G" 200 C. 5000g                                                   Notched Izod Impact                                                                          NB    NB   NB      NB  NB      NB     NB     NB                ft. - lbs/in. 1/2 × 1/8                                                                >6.6  >7.1 >7.9                                                                              3.31                                                                              >7.3                                                                              >8.3                                                                              2.12                                                                              >8.8   >8.1                     Heat Deflection Temp.                                                         ° F. at 264 psi                                                        Annealed at 180° F.                                                    Concentrate Compounding                                                       Temperature, ° F.                                                                     400   400  400 400 400 400 450 400    400    400               Injection Molding                                                             Temperature, ° F.                                                                     430   450-410                                                                            410 410 410 410 410 410    430    410               Gardner Color Value, Δ E                                                After 100 hours, Xenon Arc                                                                   0.4   9.8  8.5 4.4 2.1 7.5 3.9 1.3    3.0    2.4               __________________________________________________________________________

Referring to Tables III through XVI in general, it is readily apparentthat the incorporation of additives in polymer systems is highlyunpredictable. Even in the same polymer, "structurally related" priorart compounds and the bis-phenoxy compounds (of the present invention)produced completely different results. For example, Table III shows theresults of testing an ABS polymer containing 15% PAC or BPC and 5% EA.The ABS/BPC/EA combination is the only one which produced V-O (UL 94),white color ΔE values substantially the same as the control (withoutadditives) and superior thermal stability. White B,C,D, and F (prior artcompounds) yielded a V-O (UL 94) composition, the ΔE values wereexcessively high and thus non-applicable for commerical ABS uses. A andE show non-efficacy (HB ratings like the control) thereof as flameretardants and again point out the non-predictability of additivesincorporated in either the same or various polymers. (The inclusion ofdata, relating to where no enhancing agent is used, is presented to shownon-efficacy of BPC at low concentrations and the large quantitiesrequired to produce efficacy--note Tables IV and V.) Thus, out of allthe data shown herein, (Examples I through VIII), it is clear that thecombination of the bis-phenoxy compounds and enhancing agent result inan unexpected, superior, flame retarded epoxy resin composition whichhas commercial application as compared to most other polymers.

EXAMPLE IX

Solid samples of epoxy resin laminates separately containing certainprior art compounds and the herein described bis-phenoxy compounds, bothwith the herein described enhancing agents, are prepared according tothe above-described procedure of Example I, except that the final testspecimens consist of 3 plies of a fiber glass mat (i.e. 11/2 ounce persquare foot chopped strand mat). The epoxy resin (Epon 828), enhancingagent and curing agent (in this example - triethylenetetraamine, 12parts by weight--phr) which are in a liquid form, are applied to saidfiber glass mats in an amount to provide an end product (test specimen)which consists of 25.8% glass. The specimens are placed in an oven andcured for 24 hours at 25° C. and then for 1 hour at 100° C. The curedspecimens are subjected to the same test as described in the aforegoingExamples I and VIII in addition to the following tests in order toascertain comparative properties of the resultant epoxy resin laminates:

    ______________________________________                                        (1)  Flexural Strength and                                                                           : ASTM Test No. D-790                                       Modulus of Elasticity                                                    ______________________________________                                    

This ASTM Test No. D-790 is to be considered as incorporated herein byreference. The results of this comparative testing are shown in TablesXVII and XVIII.

                                      Table XVII                                  __________________________________________________________________________                    Control                                                                           Prior Art               Present Invention                 Resin EPOXY     (Base                                                                             Compounds               Compounds                         Additive 10 (phr)                                                                             Resin)                                                                             A   B   C   D   E   F   III                                                                               II  VI                       __________________________________________________________________________    % Halogen/% Sb.sub.2 O.sub.3                                                                   o/o                                                                              6.2/4.2                                                                           7.4/2.3                                                                           7.7/2.4                                                                           7.5/2.3                                                                           5.0/1.5                                                                           6.5/2.0                                                                           6.1/1.9                                                                           6.2/1.9                                                                           7.1/2.2                   Oxygen Index, %                                                               at 73° F.                                                                               22.8                                                                             33.3                                                                              26.5                                                                              26.3                                                                              25.5                                                                              24.3                                                                              24.5                                                                              26.5                                                                              25.8                                                                              26.3                      Flexural Strength, psi                                                        (pounds per square inch)                                                                      21,000                                                                            11,800                                                                            9,100                                                                             13,800                                                                            11,800                                                                            12,300                                                                            11,500                                                                            10,700                                                                            11,500                                                                            12,300                    Modulus of Elasticity                                                                         0.516                                                                             0.485                                                                             0.473                                                                             0.489                                                                             0.511                                                                             0.500                                                                             0.499                                                                             0.464                                                                             0.493                                                                             0.509                     (psi × 10.sup.-.sup.6)                                                  Heat Distortion Temperature                                                   ° C. at 264 psi                                                                         90  98  99  100                                                                               94  93  101                                                                               94  97  99                       Annealed at 180° F.                                                    TGA, % wt. loss at 180° C.                                             after 7 days     1.52                                                                              2.42                                                                              3.00                                                                             4.28                                                                              3.93                                                                              2.29                                                                              4.40                                                                              4.52                                                                              4.19                                                                              3.68                      __________________________________________________________________________

                                      Table XVIII                                 __________________________________________________________________________                  Control                                                                           Prior Art                     Present Invention             Resin EPOXY   (Base                                                                             Compounds                     Compounds                     Additive 20 (phr)                                                                           Resin)                                                                             A    B    C    D    E    F    III  II   VI                 __________________________________________________________________________    % Halogen/% Sb.sub.2 O.sub.3                                                                 o/o                                                                              11.0/7.5  13.9/4.2  9.1/2.8   11.0/3.4  12.8/3.9                                   13.3/4.1  13.5/4.2  11.8/3.6  11.2/3.4                 Oxygen Index, %                                                               at 73° F.                                                                            22.8                                                                              39.5 36.0 36.0 31.5 30.3 30.5 33.5 33.3 35.0                Flexural Strength, psi                                                        (pounds per square inch)                                                                    21,000                                                                            10,900                                                                             6,900                                                                              8,600                                                                              9,500                                                                              10,100                                                                             8,700                                                                              9,100                                                                              9,700                                                                              10,400              Modulus of Elasticity                                                         (psi × 10.sup.-.sup.6)                                                                0.516                                                                             0.499                                                                              0.515                                                                              0.491                                                                              0.530                                                                              0.515                                                                              0.521                                                                              0.470                                                                              0.492                                                                              0.539               Heat Distortion Temperature                                                   ° C. at 264 psi                                                                       90  97   95   89   90   96   100  93   96   99                 Annealed at 180° F.                                                    TGA % wt. loss at 180° C.                                              after 7 days  1.52                                                                              2.24 2.68 5.66 5.27 4.78 10.13                                                                              6.58 3.10 2.50                __________________________________________________________________________

Referring to Tables XVII and XVIII, the "phr" means "parts per hundredresin basis." The "Halogen" is bromine and the ratios shown, while nothaving the same numerical values, all result in having a ratio ofHalogen to Sb₂ O₃ of 6:1 and thus are all on an equivalent basis.

The results shown in each of these tables demonstrate flame retardantefficacy of the present invention compounds (e.g. Formulae II, III andVI) in an epoxy resin laminate. While the flexural strength of thecontrol (i.e. o/o -0% Halogen/0% Sb₂ O₃) was approximately 21,000 psi,the addition of both the prior art compounds and the present inventioncompounds did lower this value to some degree; however, the resultantepoxy resin laminates still have commercial utility.

EXAMPLE X

The procedure of Examples I and II are repeated except that thebis-phenoxy compound used corresponds to Formula VI heretofor set forth,instead of Formulae II and III. Substantially the same results areobtained using the Formula VI compound as those obtained using theFormulae II and III compounds.

EXAMPLE XI

The procedure of Examples VII, VIII, IX and X are repeated except thatthe enhancing agent used is zinc borate instead of antimony oxide.Substantially the same results are obtained using zinc borate as thoseusing antimony oxide.

EXAMPLE XII

The bis-phenoxy compounds described herein are subjected to toxicitytests and it is found that these compounds are not toxic orally, notirritating to the eye and not irritating to the skin, all as measured bythe guidelines of the Federal Hazardous Substances Act. Furthermore, ratfeeding studies indicate these materials are not biologicallypersistent, an important property to minimize ecological imbalance.

In summary, the results shown in Tables III through XVIII (in additionto those set forth in Example I) are reviewed with the aforementionedcriteria, i.e. UL 94 rating V-O and physical properties such as thermalstability, and are presented in Table XIX in terms of whether there iscommercial utility (taking into consideration all physical andmechanical properties), i.e. similar to those results shown foroctabromobiphenyl in Modern Plastics Encyclopedia, ibid. Table XIX setsforth more vividly the difference between the present invention and theprior art and also the different results obtained when differentpolymers have the same additives incorporated therein; and alsoconfirming these specific observations regarding the difference inpolymer systems as noted by the Norris et al. paper, ibid.

                                      TABLE 212                                   __________________________________________________________________________    FLAME RETARDANT EFFICACY OF DIFFERENT ADDITIVES IN DIFFERENT POLYMER          SYSTEMS                                                                       (IS THERE COMMERCIAL UTILITY BASED ON AN EPOXY RESIN SYSTEM CRITERIA?)                       Prior Art        Present Invention                             Polymers       Compounds + Enhancing Agents                                                                   Compounds + Enhancing Agents                  I. Present Invention                                                                         A  B  C  D  E  F II III                                                                              VI IV VIII                                                                             IX VII                         __________________________________________________________________________    Epoxy Resin                     Yes                                                                              Yes                                                                              Yes                                                                              Yes                                  II. Comparative Polymers                                                      Polystyrene (HIPS)                                                                           No                                                                              ?* ?* ?* No No No No Yes      No Yes                         Polycarbonate  No                                                                              ?* No No Yes                                                                              No Yes                                                                              Yes                                                                              Yes                                     Nylon          No                                                                              Yes                                                                              No    No    No No Yes                                     Polypropylene  No                                                                              No No No No Yes                                                                              No No No                                      Polyester      No                                                                              No Yes                                                                              Yes                                                                              Yes                                                                              No No No Yes                                     Polyphenylene oxide (PPO)                                                                      Yes                                                                              Yes                                                                              Yes                                                                              Yes                                                                              yes                                                                              Yes                                                                              Yes                                                                              Yes                                     Polyethylene (LDPE)                                                                            ?* No No No No No Yes                                                                              Yes      No                             Polyacrylonitrile               No No                                         Polymethylmethacrylate          No No                                         ABS            No                                                                              ?* ?* ?* No Yes                                                                              Yes                                                                              Yes                                                                              Yes                                                                              Yes                                                                              Yes                                                                              Yes                            __________________________________________________________________________     *Perhaps Δ E values very high                                      

In view of the foregoing Examples and remarks, it is seen that theplastic compositions, which incorporate a three component system(including the bis-phenoxy compounds), possess characteristics whichhave been unobtainable in the prior art. Specifically, the use ofbis-phenoxy compounds and enhancing agents in epoxy resin as flameretardants therefor is quite unique since it is not possible to predictthe effectiveness and functionality of any particular material in anypolymer system until it is actively undergone incorporation therein andthe resultant plastic composition evaluated according to certaincriteria such as UL-94 and various ASTM Standards. Furthermore, it isnecessary, in order to have commercial utility, that the resultant flameretarded plastic composition possess characteristics such as beingnon-toxic and not biologically persistent. Use of the bis-phenoxycompounds and an enhancing agent in an epoxy resin has accomplished allof these objectives.

Thus, in order to meet the needs and standards of commerce, it isnecessary that a successful candidate fulfill all of the requirementsoutlined above, not just a selected group. It was totally unexpectedthat this specific group of bis-phenoxy compounds meet theserequirements in all aspects contrary to the expectations of thesuggested teachings of the prior art.

The above examples have been described in the foregoing specificationfor the purpose of illustration and not limitation. Many othermodifications and ramifications will naturally suggest themselves tothose skilled in the art based on this disclosure. These are intended tobe comprehended as within the scope of this invention.

What is claimed is:
 1. A plastic composition comprising a threecomponent system consisting of (1) an epoxy resin polymer, (2) abis-phenoxy compound, which functions as a flame retardant for saidcomposition, having the formula ##STR19## wherein (a) Z is bromine; (b)m and m' are independent and are integers having a value of from 1 to 5with the proviso that the bromine atom content is from 6 to 10 bromineatoms; and (c) T is a straight or branched chain carbon group havingfrom one to four carbon atoms, and (3) a flame retardant enhancingagent.
 2. The composition as set forth in claim 1 wherein the amount ofsaid bis-phenoxy compound employed is from about 1% to about 25% byweight, based on the total weight of said composition.
 3. Thecomposition as set forth in claim 2 wherein the T is CH₂.
 4. Thecomposition as set forth in claim 2 wherein the T is (CH₂)₂.
 5. Thecomposition as set forth in claim 2 wherein the T is (CH₂)₃.
 6. Thecomposition as set forth in claim 2 wherein the T is (CH₂)₄.
 7. Thecomposition as set forth in claim 2 wherein the T is ##STR20##
 8. Thecomposition as set forth in claim 2 wherein the T is ##STR21##
 9. Thecomposition as set forth in claim 2 wherein the enhancing agent isselected from the group consisting of oxides and halides of Groups IV Aand V A of the Periodic Table of Elements.
 10. The composition as setforth in claim 9 wherein the T is (CH₂)₂ and m and m' are each
 5. 11.The composition as set forth in claim 9 wherein the T is (CH₂)₂ and mand m' are each
 3. 12. The composition as set forth in claim 9 whereinthe T is (CH₂)₃ and m and m' are each
 3. 13. The composition as setforth in claim 9 wherein the T is (CH₂)₄ and m and m' are each
 3. 14.The composition as set forth in claim 9 wherein the T is CH₂ and m andm' are each
 3. 15. The composition as set forth in claim 9 wherein the Tis CH₂ and m and m' are each
 5. 16. The composition as set forth inclaim 9 wherein the T is (CH₂)₂ and m is 5 and m' is
 3. 17. Thecomposition as set forth in claim 9 wherein the enhancing agent isantimony oxide.
 18. A flame retarded, shaped plastic compositioncomprising a three component system which consists of (a) an epoxyresin, (b) a bis-phenoxy compound selected from the group consisting of(i) 1,2-bis(2,4,6-tribromophenoxy)ethane, (ii)1,3,-bis(2,4,6-tribromophenoxy)propane and (iii)1,2,-bis(2,3,4,5,6-pentabromophenoxy)ethane and (c) an enhancing agentselected from the group consisting of oxides of antimony, arsenic andbismuth; with the proviso that said plastic composition is furthercharacterized by having a flammability rating of SE-O (V-O) asdetermined by the UL 94 procedure described in the specification. 19.The composition as set forth in claim 18 wherein (a) the bis-phenoxycompound is 1,2-bis(2,4,6-tribromophenoxy)ethane and is present in anamount of from about 1% by weight to about 20% by weight, based on thetotal weight of said composition and (b) the enhancing agent is antimonytrioxide and is present in an amount of from about 1% by weight to about10% by weight, based on the total weight of said composition.
 20. Acomposition as set forth in claim 19 wherein the amount of saidbis-phenoxy compound is about 3% by weight, based on the total weight ofsaid composition, and said enhancing agent is present in an amount ofabout 3% by weight, based on the total weight of said composition.
 21. Acomposition as set forth in claim 19 wherein the amount of saidbis-phenoxy compound is about 10% by weight, based on the total weightof said composition, and said enhancing agent is present in an amount ofabout 5% by weight, based on the total weight of said composition. 22.The composition as set forth in claim 18 wherein (a) the bis-phenoxycompound is 1,3-bis(2,4,6-tibromophenoxy)propane and is present in anamount of from about 1% by weight to about 20% by weight, based on thetotal weight of said composition and (b) the enhancing agent is antimonytrioxide and is present in an amount of from about 1% by weight to about10% by weight, based on the total weight of said composition.
 23. Acomposition as set forth in claim 22 wherein the amount of saidbis-phenoxy compound is about 10% by weight, based on the total weightof said composition, and said enhancing agent is present in an amount ofabout 5% by weight, based on the total weight of said composition.
 24. Acomposition as set forth in claim 22 wherein the amount of saidbis-phenoxy compound is about 12.5% by weight, based on the total weightof said composition, and said enhancing agent is present in an amount ofabout 5% by weight, based on the total weight of said composition.
 25. Acomposition as set forth in claim 18 wherein (a) the bis-phenoxycompound is 1,2-bis(2,3,4,5,6-pentabromophenoxy)ethane and is present inan amount of from about 1% by weight to about 20% by weight, based onthe total weight of said composition and (b) the enhancing agent isantimony trioxide and is present in an amount of from about 1% by weightto about 10% by weight, based on the total weight of said composition.26. A composition as set forth in claim 25 wherein the bis-phenoxycompound is present in an amount of about 10% by weight, based on thetotal weight of said composition and the enhancing agent is present inan amount of about 5% by weight based on the total weight of saidcomposition.